Condensation-curing compositions containing siloxane-imide base polymers

Abstract

This article shows and describes a condensation-curing silicone adhesive composition comprising a siloxane-imide base polymer, a condensation-curing organic-based polysiloxane crosslinking agent, a condensation catalyst, and additives. The composition is curable at relatively room temperature and exhibits good thermal stability.

Description

Technical Field

[0001] This invention relates to condensation-curing compositions. In particular, it relates to curable compositions comprising a siloxane-imide base polymer, a crosslinking agent, a catalyst, and optionally other additives. The compositions can be cured at room temperature in less than 24 hours, and the cured materials exhibit stability to extreme temperature conditions (e.g., even at 350°C or higher) for use in a variety of applications. Background Technology

[0002] Highly thermally stable materials, such as those stable at approximately 350°C or higher, are desirable for a wide range of applications. Furthermore, many applications require not only stability at high temperatures but also the ability for materials to maintain or substantially retain their mechanical properties and flexibility over a wide temperature range, from extremely cold (e.g., below 0°C to -100°C) to high-temperature exposure (e.g., approximately 350°C or higher). Many current curable silicone-based materials are generally stable only up to 275°C.

[0003] Current silicone-based materials used in the aerospace industry maintain their elastomeric properties continuously from -115°C (-175°F) to up to 260°C (500°F), and can even retain these properties for short periods up to 316°C (600°F). Organic polymers such as polyimides and polybenzimidazoles are stable above 400°C, but these materials have their own processability and flexibility issues, making them unsuitable for some applications. Given their respective limitations (thermal stability and flexibility), pure silicone resins or pure organic polymers such as polyimides cannot be used alone for such wide-temperature applications.

[0004] Siloxane-modified polyimide materials are known in the art. These materials are self-supporting film flexible materials with high thermal stability and high thermal conductivity. However, these materials have some processability issues that limit their ability to be used in large-scale applications.

[0005] Recent attempts to improve thermal stability have included the use of mold-making compositions comprising copolymers of siloxane-modified polyimides or siloxane-polyetherimide block copolymers (see, for example, U.S. Patent Nos. 8,071,693, 2003 / 0004268, and 6,451,381). Other attempts are described, for example, in Japanese Patents 3279635 and 4803371 relating to non-curing siloxane-imide copolymers and Korean Patent Publication 10-2014-007363 relating to composite sheets comprising siloxane-imide copolymers and reinforcing materials. However, these proposed solutions do not address materials with high thermal stability above 350°C. Summary of the Invention

[0006] The following summary of the invention is presented to provide a basic understanding of some aspects. This summary is not intended to identify key or decisive elements, nor is it intended to define any limitations on the implementation or claims. Furthermore, the summary provides a simplified overview of aspects that can be described in more detail in other parts of this disclosure.

[0007] We provide a condensation-curable organosilicon-imide composition that has been found to cure at room temperature for 24 hours in the absence of any solvent, and a cured material containing the composition that exhibits superior thermal stability compared to pure siloxanes.

[0008] In one aspect, a condensation-curing composition is provided, comprising: (a) an organosilicon-imide base polymer; (b) a crosslinking agent; (c) a condensation-curing catalyst; and (d) optionally, an additive.

[0009] In one embodiment, the organosilicon-imide base polymer (a) is selected from compounds of formula (I):

[0010]

[0011] Where R 1 Selected from C5-C20 aryl groups, polycyclic aryl groups containing two or more C5-C20 aryl groups, wherein R 1 It may be unsubstituted or substituted with C1-C6 alkyl, halogen, haloalkyl, hydroxy and / or C1-C5 alkoxy groups;

[0012] C 1 It can be selected from C1 to C5 alkyl, C5-C20 aryl, C7-C16 arylalkyl or C7-C16 alkylaryl;

[0013] R 2 R 3 and R4 They can be the same or different, and can be selected from C1-C3 alkyl or phenyl;

[0014] R 5 They can be the same or different, and can be selected from C1-C30 alkyl, C1-C30 alkoxy, C1-C30 acyloxy or C1-C30 ketoxime groups;

[0015] m is an integer between 1 and 30; and

[0016] n is an integer between 1 and 200.

[0017] In one implementation, R 1 The compound is selected from benzene, naphthalene, benzophenone, biphenyl, diphenylalkanes, diphenyl ethers, isopropylidene diphenylphenoxy, diphenyl sulfone, diphenyl sulfide, norbornel, and hexafluoromethylbiphenyl. In one embodiment, R 1 It is benzene.

[0018] In one embodiment of the curable silicone composition described in any of the foregoing embodiments, the silicone-imide base polymer (a) is present in an amount of about 20 parts to about 100 parts, about 40% by weight to about 95% by weight, or about 50% by weight to about 91% by weight, based on the total weight parts of the curable silicone composition.

[0019] In one embodiment, the crosslinking agent (b) is selected from alkoxysilanes, alkoxysilates, alkoxysiloxanes, oximosilanes, enoxysilanes, aminosilanes, carboxylsilanes, carboxylsiloxanes, alkylamide silanes, alkylamide siloxanes, arylamide silanes, arylamide siloxanes, alkoxyaminosilanes, alkylarylamide siloxanes, alkoxycarbamatosilanes, alkoxycarbamatosilanes, and combinations of two or more thereof.

[0020] In any of the foregoing embodiments of the curable silicone composition, the crosslinking agent (b) is selected from tetraethyl orthosilicate (TEOS), methyltrimethoxysilane (MTMS), or a combination thereof.

[0021] In one embodiment of the curable silicone composition described in any of the foregoing embodiments, the crosslinking agent (b) is present in an amount of about 0.5 parts to about 50 parts, about 1 part to about 30 parts, or about 5 parts to about 10 parts, based on the total weight parts of the curable silicone composition.

[0022] In one embodiment of the curable organosilicon composition described in any of the foregoing embodiments, the catalyst (c) is selected from tin catalysts such as dibutyltin dilaurate (DBTDL) or dioctyltin compounds, metal or organometallic catalysts comprising, for example, the following metals: Ca, Ce, Bi, Fe, Mo, Mn, Pb, Ti, V, Zn and Y, and non-tin catalysts comprising combinations of: carboxylic acid components, amino-containing silanes or mixtures of amino-containing silanes, and optionally amino-containing siloxane components.

[0023] In one embodiment of the curable organosilicon composition of any of the foregoing embodiments, the organometallic catalyst is dibutyltin dilaurate.

[0024] In one embodiment of the curable silicone composition described in any of the foregoing methods, the catalyst (c) is present in an amount of about 0.01 parts to about 5 parts, about 0.2 parts to about 1 part, or about 0.01 parts to about 0.03 parts, based on the total weight parts of the curable silicone composition.

[0025] In any of the foregoing embodiments of the curable silicone composition, the additive (d) is selected from fillers, pigments, lubricants, viscosity modifiers, antioxidants, light stabilizers, heat stabilizers, flame retardants, inhibitors, adhesion promoters, or combinations of two or more thereof.

[0026] In any of the foregoing embodiments of the curable silicone composition, the additive is a filler.

[0027] In any of the foregoing embodiments of the curable organosilicon composition, the filler is selected from SiO2, TiO2, MgO, ZnO, CaCO3, CeO2, Fe2O3, SiC, clay materials, graphene oxide, boron oxide, BN, carbon nanotubes, zirconium oxide, fly ash, Zr(OEt)4, Ti(OEt)4, polyimide, polybenzimidazole, polyamide-imide, polyBPA sulfone, siloxane-polyimide, siloxane-benzimidazole, siloxane-polysulfone in powder form, or any other thermally stable filler.

[0028] In any of the foregoing embodiments of the curable silicone composition, the amount of the filler is about 0 parts to about 50 parts, about 15 parts to about 40 parts, or about 25 parts to about 30 parts by weight, based on the total weight of the curable silicone composition.

[0029] In one embodiment of the curable organosilicon composition described in any of the foregoing embodiments, the filler is Fe2O3.

[0030] In one embodiment, the organosilicon-imide composition according to any of the foregoing embodiments is coated or adhered to a substrate.

[0031] In one embodiment, the substrate is selected from plastic materials, ceramics, glass, rubber materials, filled metal, metal alloys, metallized plastics, and / or coated or painted metals.

[0032] In one embodiment, the composition is used to form a cured organosilicon-imide material.

[0033] In one embodiment, a cured organosilicon-imide material formed from the composition is provided, which exhibits thermal degradation at 400°C to 600°C as measured by thermogravimetric analysis.

[0034] In another embodiment, the cured organosilicon-imide material formed from the composition is used in aerospace, electronics, automotive, insulation, coating, and solvent-resistant film applications.

[0035] The following description and figures disclose various illustrative aspects. Some improvements and novel aspects can be clearly identified, while others are self-evident from the description and figures. Detailed Implementation

[0036] Exemplary embodiments will now be described, examples of which are illustrated in the accompanying drawings. It should be understood that other embodiments may be utilized and structural and functional changes may be made. Furthermore, features of various embodiments may be combined or modified. Therefore, the following description is presented merely by way of illustration and should in no way limit the various alternatives and modifications that may be made to the illustrated embodiments. Numerous specific details in this disclosure provide a thorough understanding of the subject matter. It should be understood that aspects of this disclosure may be practiced using other embodiments, not necessarily including all aspects described herein.

[0037] As used herein, the terms “example” and “exemplary” mean illustrative or exemplary. The terms “example” or “exemplary” do not indicate key or preferred aspects or implementations. The term “or” is intended to be inclusive rather than exclusive unless the context otherwise requires. As an example, the phrase “A employs B or C” includes any inclusive permutation (e.g., A employs B; A employs C; or A employs both B and C). As another matter, the articles “a” and “an” are generally intended to mean “one or more” unless the context otherwise requires.

[0038] This disclosure identifies multiple distinct ranges for one or more components in a composition. It will be understood that values ​​for these ranges can be combined to form new and undisclosed ranges.

[0039] The term "alkyl" includes straight, 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. Examples of suitable alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, etc.

[0040] The term "alkylene" includes straight, branched, and cyclic divalent hydrocarbon groups, which may be substituted with heteroatoms or heteroatom-containing groups. In embodiments, the term alkylene includes C1-C30 alkylene groups. Examples of alkylene include, but are not limited to, methylene, ethylene, propylene, isopropylene, butylene, isobutylene, tert-butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, etc.

[0041] The term "aryl" includes any monovalent aromatic hydrocarbon group, which may be substituted with heteroatoms or heteroatom-containing groups. The term also includes fused systems comprising aromatic groups and groups having multiple aryl groups linked by bonds or linking groups. In embodiments, the term aryl includes C5-C20 aryl groups, fused aryl groups comprising two or more C5-C20 aryl groups, and polyaryl group structures comprising two or more C5-C20 aryl groups linked by linking groups.

[0042] The term "aryl" includes any divalent aromatic hydrocarbon group, which may be substituted with a heteroatom or a heteroatom-containing group. The term also includes fused systems containing aromatic groups. In embodiments, the term aryl includes C5-C20 aryl groups, fused aryl groups comprising two or more C5-C20 aryl groups, and polyaryl group structures comprising two or more C5-C20 aryl groups linked by a linking group.

[0043] The term "aralkyl" includes straight, branched, and cyclic monovalent hydrocarbon groups substituted with aryl substituents.

[0044] The term "cyclic" or "cyclic" alkyl includes monovalent cyclic hydrocarbons and includes free cyclic groups, bicyclic groups, tricyclic groups, and higher cyclic structures, as well as bridging cyclic groups, fused cyclic groups, and fused cyclic groups containing at least one bridging cyclic group. In embodiments, cyclic alkyl groups include C3-C20 cyclic alkyl groups. Examples of suitable cyclic groups include, but are not limited to, cyclopropyl, cyclopentyl, cyclohexyl, norcamphenyl, bicyclic [2.2.2]nonane, adamantyl, or tetrahydronaphthyl (1,2,3,4-tetrahydronaphthyl).

[0045] The term "cyclic" or "cyclic" alkylene includes divalent cyclic hydrocarbons and includes free cyclic groups, bicyclic groups, tricyclic groups, and higher cyclic structures, as well as bridging cyclic groups, fused cyclic groups, and fused cyclic groups containing at least one bridging cyclic group. In embodiments, cyclic alkylene includes C3-C20 cyclic alkylene groups.

[0046] The term "alkynyl" is defined as a C2-C10 branched or straight-chain unsaturated aliphatic hydrocarbon group having one or more triple bonds between two or more carbon atoms. Examples of alkynyl groups include ethynyl, propynyl, butynyl, penynyl, hexynyl, hepynyl, octyynyl, and nonynyl.

[0047] The term "substituted" means that one or more hydrogen atoms or atoms on a molecule or molecular moiety are replaced by a substituent, provided that the valence does not exceed the normal valence. Substituents can be heteroatoms. The term "heteroatomic" as used refers to atoms, or groups combined with another group containing atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, boron, etc. Examples of suitable substituents include, but are not limited to, —OR, —NR′R, —C(O)R, —SR, —halogenated, —CN, —NO2, —SO2, phosphoryl, imino, thioester, carboxyl, aryl, heteroaryl, alkyl, alkenyl, bicyclic, and tricyclic groups. When the substituent is a ketone group (i.e., ═O), two hydrogen atoms on the atom are replaced. Ketone substituents are not present on the aromatic moiety. The terms R and R′ refer to alkyl groups, which may be the same or different.

[0048] A condensation-curable organosilicon-imide composition that has been found to cure at room temperature in the absence of any solvent is provided. The condensation-curable composition comprises a siloxane-imide base polymer. Cured materials comprising or formed from the said curable composition are also provided. For example, its decomposition peak (T0) is evaluated using thermogravimetric analysis. d As confirmed by [the study], the cured material exhibits excellent thermal stability. The thermal stability of the cured material formed from the composition is superior to that of pure siloxanes.

[0049] In one aspect, a condensation-curing composition is provided, comprising: (a) an organosilicon-imide base polymer; (b) a crosslinking agent; (c) a condensation-curing catalyst; and (d) optionally, an additive.

[0050] In one embodiment, the organosilicon-imide base polymer (a) is selected from compounds of formula (I):

[0051]

[0052] Where R 1Selected from C5-C20 aryl groups, polycyclic aryl groups containing two or more C5-C20 aryl groups, wherein R 1 It may be unsubstituted or substituted with C1-C6 alkyl, halogen, haloalkyl, hydroxy and / or C1-C5 alkoxy groups;

[0053] C 1 It can be selected from C1 to C5 alkyl, C5-C20 aryl, C7-C16 arylalkyl or C7-C16 alkylaryl;

[0054] R 2 R 3 and R 4 They can be the same or different, and can be selected from C1-C3 alkyl or phenyl;

[0055] R 5 They can be the same or different, and can be selected from C1-C30 alkyl, C1-C30 alkoxy, C1-C30 acyloxy or C1-C30 ketoxime groups;

[0056] m is an integer between 1 and 30; and

[0057] n is an integer between 1 and 200.

[0058] R 1 Selected from C5-C20 aryl groups or polycyclic aryl groups containing two or more C5-C20 aryl groups. The polycyclic aryl groups can be fused rings or non-fused systems linked by linking groups. For R 1 Examples of suitable aryl and / or polycyclic aryl groups include, but are not limited to, benzene, naphthalene, benzophenone, biphenyl, diphenylalkanes (e.g., diphenyl groups having alkyl linkages selected from C1-C20 alkyl groups, such as, but not limited to, diphenylmethane, diphenylethane, diphenylpropane, diphenylisopropane, diphenylbutane, diphenylisobutene, diphenyltert-butane, diphenylhexane, diphenyloctane, etc.), diphenyl ethers, isopropylidene diphenylphenoxy, diphenyl sulfone, diphenyl sulfide, norbornel, and hexafluoromethyl biphenyl, etc. In one embodiment, R 1 It is benzene.

[0059] R 2 R 3 and R 4 It can be the same or different, and can be selected from C1 to C3 alkyl or phenyl. In one embodiment, R 2 R 3 and R 4 Each is a methyl group. In one embodiment, R 2 and R 4 Each is a C1-C3 alkyl group, and R 3 It is a phenyl group.

[0060] R 5 They can be the same or different, and can be selected from C1-C30 alkyl, C1-C30 alkoxy, C1-C30 acyloxy, or C1-C30 ketoxime groups. In the embodiments, each R 5 The components are independently selected from C1-C10 alkyl, C2-C8 alkyl, or C4-C6 alkyl. In one embodiment, each R... 5 It is a methyl group.

[0061] The variable m can be 1-30, 2-25, 5-20, 6-15, or 8-10. In one implementation, m is 1.

[0062] The variable n can be 1-200, 5-150, 10-125, 25-100, or 50-75.

[0063] The crosslinking agent (b) may be selected according to the needs of a specific purpose or intended application. The crosslinking agent (b) is generally selected from silicone-based materials. Examples of suitable materials as crosslinking agents (b) include, but are not limited to, alkoxysilanes, alkoxysilicates, alkoxysiloxanes, oximesilanes, oximesiloxanes, alkenoxysilanes, alkenoxysiloxanes, aminosilanes, carboxylsilanes, carboxylsiloxanes, alkylamide silanes, alkylamide siloxanes, arylamide silanes, arylamide siloxanes, alkoxyaminosilanes, alkylarylamide siloxanes, alkoxycarbamate silanes, alkoxycarbamate siloxanes, and combinations of two or more thereof.

[0064] Examples of suitable crosslinking agents include, but are not limited to, tetraethyl orthosilicate (TEOS); methyltrimethoxysilane (MTMS); methyltriethoxysilane; vinyltrimethoxysilane; vinyltriethoxysilane; methylphenyldimethoxysilane; 3,3,3-trifluoropropyltrimethoxysilane; methyltriacetoxysilane; vinyltriacetoxysilane; ethyltriacetoxysilane; dibutoxydiacetoxysilane; phenyltripropionyloxysilane; methyltris(methylethylketoxime)silane; vinyltris(methylethylketoxime)silane; 3,3,3-trifluoropropyltris(methylethylketoxime)silane; methyltris(isopropenoxy)silane; vinyltris(isopropenoxy)silane; ethyl polysilicate. (ethylpolysilicate); dimethyltetraacetoxydisiloxane; tetra-n-propyl orthosilicate; methyldimethoxy(ethylmethyl ketoxime)silane; methylmethoxybis-(ethylmethyl ketoxime)silane; methyldimethoxy(acetaldoximo)silane; methyldimethoxy(N-methylcarbamate)silane; ethyldimethoxy(N-methylcarbamate)silane; methyldimethoxyisopropenoxysilane; trimethoxyisopropenoxysilane; methyltriisopropenoxysilane; methyldimethoxy(but-2-en-2-oxy)silane; methyldimethoxy(1-phenylvinyloxy)silane; methyldimethoxy-2(1 -Carboxyethoxypropenyloxy)silane; Methylmethoxydi-N-methylaminosilane; Vinyldimethoxymethylaminosilane; Tetra-N,N-diethylaminosilane; Methyldimethoxymethylaminosilane; Methyltricyclohexylaminosilane; Methyldimethoxyethylaminosilane; Dimethyldi-N,N-dimethylaminosilane; Methyldimethoxyisopropylaminosilane; Dimethyldi-N,N-diethylaminosilane; Ethyldimethoxy(N-ethylpropionylamino)silane; Methyldimethoxy(N-methylacetamido)silane; Methyltris(N-methylacetamido)silane; Ethyldimethoxy(N-methylacetamido)silane; Methyltris(N-methylbenzoylamino)silane; Methylmethoxy Bis(N-methylacetamido)silane; methyldimethoxy(caprolactam)silane; trimethoxy(N-methylacetamido)silane; methyldimethoxyethylacetimidatosilane; methyldimethoxypropylacetimidatosilane; methyldimethoxy(N,N′,N′-trimethylurea)silane; methyldimethoxy(N-allyl-N′,N′-dimethylurea)silane; methyldimethoxy(N-phenyl-N′,N′-dimethylurea)silane; methyldimethoxyisocyanosilane; dimethoxydiisocyanosilane; methyldimethoxythioisocyanosilane; methyldimethoxydithioisocyanosilane, or combinations of two or more thereof.

[0065] The condensation-curing catalyst (c) can be used to promote the reaction of condensation-curing organo-based polysiloxanes with siloxane-imide crosslinking agents. The condensation-curing catalyst is not particularly limited and can be selected from any suitable catalyst material used to promote the condensation-curing reaction. Examples of suitable metal or organometallic catalysts include, but are not limited to, those using metals such as tin, titanium, zinc, and calcium, and complexes of these metals. Examples of suitable condensation catalysts for use in this invention include, but are not limited to, tin catalysts such as dibutyltin dilaurate (DBTDL) or dioctyltin compounds, metal or organometallic catalysts containing metals such as Ca, Ce, Bi, Fe, Mo, Mn, Pb, Ti, V, Zn, and Y, and non-tin catalysts comprising a combination of a carboxylic acid component, an amino-containing silane, or a mixture of amino-containing silanes, and optionally an amino-containing siloxane component.

[0066] The carboxylic acid component of the catalyst can be selected from any suitable carboxylic acid component. In one embodiment, the carboxylic acid component can be selected from aliphatic carboxylic acids. Suitable carboxylic acids for the carboxylic acid component include, but are not limited to, branched alkyl C4-C30 alkyl carboxylic acids, including C5-C30, or even C5-C19 acids having an α-tertiary carbon, or combinations of two or more thereof. Some useful carboxylic acids that may be used herein include, but are not limited to, propionic acid, 2-methylpropionic acid, butyric acid, valeric acid, caproic acid, 2-ethylhexanoic acid, enanthic acid, caprylic acid, oleic acid, linoleic acid, linolenic acid, cyclohexanecarboxylic acid, cyclohexylacetic acid, cyclohexenecarboxylic acid, benzoic acid, phenylacetic acid, malonic acid, succinic acid, adipic acid, 2-butenic acid, lauric acid, stearic acid, myristic acid, palmitic acid, isonononic acid, and versatic acid. TM Acid (derived from Momentive), or a combination of two or more thereof.

[0067] In one embodiment, the organometallic catalyst is dibutyltin dilaurate.

[0068] The additive (d) can be selected from a variety of additives and is chosen according to the needs of a specific purpose or intended application. Additives can be selected to impart certain properties to the cured material formed from the composition, such as to aid in the processing of the composition. In one embodiment, the additive (d) is selected from pigments, lubricants, viscosity modifiers, heat stabilizers, light stabilizers, flame retardants, inhibitors, adhesion promoters, or combinations of two or more thereof.

[0069] In one embodiment, the additive (d) is present in an amount of about 0.05 parts by weight to about 3000 parts, about 0.5 parts by weight to about 1000 parts, or about 0.05 parts by weight to about 1 part, based on the total weight of the curable silicone composition. In one embodiment, the additive is present in an amount of about 0 parts by weight to about 50 parts, more preferably about 10 parts by weight to about 40 parts, and most preferably about 25 parts by weight to about 30 parts by weight, based on the total weight of the curable silicone composition.

[0070] In one embodiment, the additive is selected from inhibitors. In one embodiment, the inhibitor is selected from olefinic unsaturated amides, aromatic unsaturated amides, alkynes, olefinic unsaturated isocyanates, olefinic siloxanes, unsaturated hydrocarbon monoesters of unsaturated acids, unsaturated hydrocarbon diesters, conjugated or isolated alkynes, hydroperoxides, ketones, sulfoxides, amines, phosphites, nitrites, diazacyclobutanes, etc. Particularly suitable inhibitors for the composition are alkynyl alcohols and maleate esters. Examples of suitable polymerization inhibitors include, but are not limited to, diallyl maleate, hydroquinone, p-methoxyphenol, tert-butylcatechol, and phenothiazine.

[0071] In one embodiment, the inhibitor is present in an amount of about 1 part by weight to about 10 parts, more preferably about 0.1 parts to about 2 parts, and most preferably about 0.05 parts to about 1 part, based on the total weight of the curable organosilicon-imide composition.

[0072] In one embodiment, the additive (d) is selected from polymerization inhibitors. The polymerization inhibitors are not particularly limited and can be selected according to the needs of a particular purpose or intended use. Examples of suitable inhibitors include, but are not limited to, olefinic unsaturated amides, aromatic unsaturated amides, alkynes, olefinic unsaturated isocyanates, olefinic siloxanes, unsaturated hydrocarbon diesters, unsaturated hydrocarbon monoesters of unsaturated acids, conjugated or isolated alkynes, hydroperoxides, ketones, sulfoxides, amines, phosphites, nitrites, diazacyclobutanes, etc. Particularly suitable inhibitors for the composition are alkynyl alcohols and maleate esters. Examples of suitable polymerization inhibitors include, but are not limited to, diallyl maleate, hydroquinone, p-methoxyphenol, tert-butylcatechol, phenothiazine, etc.

[0073] The amount of inhibitor to be used in the composition can be any amount that delays (blocks) the above reaction at room temperature but does not prevent the reaction at moderately elevated temperatures. In embodiments, the polymerization inhibitor may be present in amounts 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.

[0074] The curable composition may also include antioxidant compounds. Examples of suitable classes of antioxidant compounds include, but are not limited to, hindered amines and / or hindered phenolic compounds.

[0075] Examples of hindered amine antioxidant compounds include, but are not limited to, hindered amine antioxidants (N,N′,N″,N′″-tetra-(4,6-bis(butyl-(N-methyl)-2,2,6,6-tetramethylpiperidin-4-yl)amino)-triazin-2-yl)-4,7-diazadec-1,10-diamine, dibutylamine-1,3,5-triazin-N,N′-bis-(2,2,6,6-tetramethyl-4-piperidinyl-1,6-hexamethylenediamine-N-(2,2,6,6- A condensation product of tetramethyl-4-piperidinyl)butylamine, a polymer of poly[{6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidinyl)imino}hexamethylene{(2,2,6,6-tetramethyl-4-piperidinyl)imino}], dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol, [bis(2,2,6,6-tetramethyl-1(octyloxy)] [Reaction product of )-4-piperidinyl) sebacate, 1,1-dimethylethyl hydroperoxide and octane] (70%) - polypropylene (30%), bis(1,2,2,6,6-pentamethyl-4-piperidinyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl] butyl malonate, methyl 1,2,2,6,6-pentamethyl-4-piperidinyl sebacate, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(1,2,2,6,6, 6-Pentamethyl-4-piperidinyl) 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]dec-2,4-dione, etc.).

[0076] In one embodiment, the antioxidant compound is a hindered phenolic compound. The hindered phenol may be selected according to the needs of a particular purpose or intended application. Examples of suitable hindered phenols include, but are not limited to, monophenols such as 2,6-di-tert-butyl-p-cresol, 2-tert-butyl-4-methoxyphenol, 3-tert-butyl-4-methoxyphenol, and 2,6-tert-butyl-4-ethylphenol; bisphenols such as 2,2′-methylene-bis(4-methyl-1-6-tert-butylphenol), 4,4′-thiobis(3-methyl-1-6-tert-butylphenol), and 4,4′-butylene-bis(3-methyl-1-6-tert-butylphenol); and polyphenols such as 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4- 6-Tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tetra[methylene-3-(3′,5′-di-tert-butyl-4′-hydroxyphenyl)propionate]methane, bis[3,3′-bis(4′-hydroxy-3-tert-butylphenyl)butyrate and tocopherol (vitamin E), pentaerythritol-tetra[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-hydroxyphenylpropionamide), 3,5-bis(1,1-dimethylethyl)-4-hydroxyC7-C9 alkyl ester of phenylpropionic acid, 2,4-dimethyl-6-(1-methylpentadecanyl)phenol, diethyl[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphonate, 3,3′,3″,5,5′,5″-hexane-tert-butyl-4-a,a′,a″-(trimethylmethyl-2,4,6-tolyl)tri-p-cresol, diethylbis[[[3,5-bis-(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphonic acid] Calcium, 4,6-bis(octylthiomethyl)-o-cresol, ethylenebis(oxyethylene)bis[3-(5-tert-butyl-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 product of N-phenylaniline and 2,4,4-trimethylpentene, 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazine-2-ylamino)phenol, etc.

[0077] IRGANOX 1330 is a sterically hindered phenolic antioxidant (“3,3′,3′,5,5′,5′-hexa-tert-butyl-a,a′,a′-(trimethylbenzene-2,4,6-triyl)tri-p-cresol”) commercially available from BASF. Irganox 1010 is a sterically hindered phenolic antioxidant (“pentaerythritol tetra(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate”) commercially available from BASF, or as ETHANOX. TM 330 (Albemarle Corporation) Commercially available 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (Irganox 1010), tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate (Irganox 3114), as tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate of Irganox 3114.

[0078] The antioxidant may be included in the composition in amounts of about 0 parts by weight to about 10 parts by weight, about 0 parts by weight to about 5 parts by weight, or about 0 parts by weight to about 3 parts by weight.

[0079] The curable composition may optionally include a light stabilizer. The light stabilizer is not particularly limited and may be selected according to the needs of a particular application or intended use. Examples of suitable materials for use as light stabilizers include, but are not limited to, 2,4-di-tert-butyl-6-(5-chlorobenzotriazol-2-yl)phenol, 2-(2H-benzotriazol-2-yl)-4,6-di-tert-pentylphenol, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, and 3-(3-(21-1-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl)propionic acid. The reaction products of methyl ester / polyethylene glycol 300 include 2-(2H-benzotriazol-2-yl)-6-(straight and branched dodecyl)-4-methylphenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol, octabenzone, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, Tinuvin 622LD, Tinuvin 144, Chimassorb 119FL, Mark LA-57, LA-62, LA-67, LA-63, Sandol LS-765, LS-292, LS-2626, LS-1114, LS-744, etc.

[0080] The light stabilizer may be included in the composition in amounts of about 0 parts by weight to about 10 parts by weight, about 0 parts by weight to about 5 parts by weight, or about 0 parts by weight to about 3 parts by weight.

[0081] The composition optionally includes a filler (F). In one embodiment, the additive (F) is selected from fillers. Examples of suitable fillers include, but are not limited to, silica, pyrolytic silica, SiO2, TiO2, MgO, ZnO, CaCO3, CeO2, Fe2O3, SiC, clay materials, graphene oxide, boron oxide, boron nitride (BN), carbon nanotubes, zirconium oxide, fly ash, Zr(OEt)4, Ti(OEt)4, polyimide, polybenzimidazole, polyamide-imide, polyBPA sulfone, siloxane-polyimide, siloxane-benzimidazole, siloxane-polysulfone in powder form, or any other thermally stable filler.

[0082] In one embodiment, the filler is present in an amount of about 0 parts by weight to about 3,000 parts, more preferably about 15 parts to about 2,000 parts, and most preferably about 25 parts to about 30 parts, based on the total weight of the curable silicone composition. In another embodiment, the filler may be present in an amount of about 0 parts to about 50 parts, more preferably about 10 parts to about 40 parts, and most preferably about 25 parts to about 30 parts by weight, based on the total weight of the curable silicone composition.

[0083] In one embodiment, the filler is present in an amount of about 20 parts by weight to about 30 parts by weight, based on the total weight of the curable silicone composition.

[0084] In one embodiment, the curable composition does not contain any adhesion promoter. In another embodiment, the curable composition contains an adhesion promoter.

[0085] According to one embodiment, the adhesion promoter is selected from alkoxysilanes such as aminoalkylalkoxysilanes, epoxyalkylalkoxysilanes such as 3-glycidoxypropyltrimethoxysilane and mercapto-alkylalkoxysilanes, and γ-aminopropyltriethoxysilane, the reaction product of ethylenediamine and silyl acrylate. Isocyanurates containing silicon groups, such as 1,3,5-tris(trialkoxysilylalkyl)isocyanurate, may also be used. Further suitable adhesion promoters are the reaction product of epoxyalkylalkoxysilanes such as 3-glycidoxypropyltrimethoxysilane with amino-substituted alkoxysilanes such as 3-aminopropyltrimethoxysilane and optionally alkylalkoxysilanes such as methyl-trimethoxysilane, epoxyalkylalkoxysilanes, mercaptoalkylalkoxysilanes, their derivatives, or combinations of two or more thereof.

[0086] The organosilicon-imide base polymer (a) may be present in an amount of about 20 parts to about 100 parts, more preferably about 40% to about 95% by weight, and most preferably about 50% to about 91% by weight, based on the total weight parts of the curable organosilicon composition.

[0087] The crosslinking agent (b) is present in an amount of about 0.5 parts to about 50 parts, more preferably about 1 part to about 30 parts, and most preferably about 5 parts to about 10 parts, based on the total weight parts of the curable silicone composition.

[0088] The catalyst (c) may be present in an amount of about 0.01 parts to about 5 parts, more preferably about 0.2 parts to about 1 part, and most preferably about 0.01 parts to about 0.03 parts, based on the total weight parts of the curable silicone composition.

[0089] The filler may be present in an amount of about 0 parts to about 50 parts, more preferably about 10 parts to about 40 parts, and most preferably about 25 parts to about 30 parts by weight, based on the total weight of the curable silicone composition.

[0090] The condensation-curing formulation cures in the presence of water (e.g., in the form of atmospheric moisture). When cured with water, the aforementioned hydrolysis and condensation reactions occur between the organo-based polysiloxane and the crosslinking agent, optionally assisted by a catalyst, accompanied by crosslinking to form siloxane bonds. Therefore, curing is also referred to as networking. The condensation-curing formulation of the present invention can be cured by applying the composition (as a portion of the composition or by mixing the components of two portions of the composition) to a target substrate and exposing the composition to sufficient moisture to promote curing. Curing can be carried out at room temperature (e.g., from about 20°C to about 25°C) or at elevated temperatures (e.g., above 25°C).

[0091] In one embodiment, an organosilicon-imide composition is coated or adhered to a substrate. The composition can be applied by any suitable method, including but not limited to brushing, spraying, curtain coating, dipping, spin coating, etc.

[0092] The substrate can be selected from plastic materials, ceramics, glass, rubber materials, filled metals, metallized plastics, and / or coated or painted metals. Examples of suitable plastics include, but are not limited to, synthetic organic polymers such as acrylic polymers, such as poly(methyl methacrylate); polyesters, such as poly(ethylene terephthalate), poly(butylene terephthalate); polyamides, polyimides, acrylonitrile-styrene copolymers, styrene-acrylonitrile-butadiene terpolymers, polyvinyl chloride, polyethylene, etc.; and polycarbonates and copolycarbonates such as EXL and high-temperature polycarbonates. In one embodiment, the substrate is formed from polycarbonate or acrylic resins. Polycarbonates are particularly suitable materials for transparent substrates due to their excellent physical, mechanical, and chemical properties. Generally, the choice of substrate is ultimately determined by the intended end use.

[0093] The composition can be used in a variety of applications. In embodiments, the composition can be 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 breathability, and is primarily used in aerospace, electronics, automotive, insulation, coating, solvent-resistant film applications, etc.

[0094] The cured silicone-imide material formed from the composition can exhibit thermal degradation at 300°C to 600°C, about 350°C to about 550°C, or about 400°C to 500°C. Thermal degradation, also known as thermal decomposition, can be measured by thermogravimetric analysis (TGA). In one embodiment, thermal degradation can be measured using a TA TGA Q5000. Thermal degradation can be evaluated in a nitrogen or air atmosphere at a heating rate of 10°C / min up to 1000°C. The composition can be used in a variety of applications. In embodiments, the composition can be 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 permeability, and is primarily used in aerospace, electronics, automotive, insulation, coating, solvent-resistant film applications, etc.

[0095] The organosilicon formulation comprises at least one hydroxyl- or alkoxy-terminated organo-based polysiloxane. This hydroxyl- or alkoxy-terminated organo-based polysiloxane is condensation-crosslinking. Furthermore, the hydroxyl- or alkoxy-terminated organo-based polysiloxane may contain one or more branches. However, linear hydroxyl- or alkoxy-terminated organo-based polysiloxanes are preferred. These organo-based polysiloxanes are well known to those skilled in the art.

[0096] As is conventional in the art, organosilicon formulations can be single-component or two-component organosilicon formulations. In particular, the organosilicon formulations according to the present invention are moisture-curing organosilicon formulations.

[0097] The following examples are intended to illustrate aspects and implementations of the technology. Unless otherwise expressly stated, all parts and percentages are by weight, and all temperatures are in degrees Celsius. All patents, other publications, and U.S. patent applications mentioned in this application are incorporated herein by reference in their entirety.

[0098] Example

[0099] The compositions were prepared according to the examples listed in Tables 1-2. The compositions were prepared by mixing the base polymer with a crosslinking agent and a condensation catalyst in a container. The mixtures were thoroughly mixed manually and by using a high-speed mixer.

[0100] The siloxane-imide base polymer is an ABn siloxane-polyimide material with Si-alkoxy-terminated structure (I) and synthesized as follows: from pyromellitic anhydride and allylamine, followed by the introduction of Si-H moiety and reaction with vinyltrimethoxysilane.

[0101]

[0102] Synthesis of N-allylamide of pyromellitic dianhydride: Pyromellitic dianhydride (50 g, 0.2292 mol) and acetic acid (250 mL) were placed in a three-necked round-bottom flask (condenser / top stirrer / dropping funnel), followed by dropwise addition of allylamine (28 g, 0.504 mol) under ice-cold conditions. After the addition was complete, heat was applied from 40 °C to 130 °C until the reaction mixture became a clear solution. A color change occurred over a period of time. After the solution became clear, heat was applied at 130 °C for 4 hours to form a ring. In another round-bottom flask, 250 mL of water was taken and heated at approximately 100 °C. The reaction mixture was then slowly poured into the water to form a solid material. The solid material was filtered out using a funnel with filter paper. The solid material was washed with water and methanol and dried using a high-vacuum pump. Yield = 65 g (95%). The material was characterized by 1H-NMR.

[0103] The general procedure for synthesizing Si-alkoxy-terminated ABn siloxane-imide-based polymers is as follows: Under an inert atmosphere, N-allyl-terminated pyromellitic diimide and toluene (3 times the total volume of reactants) are placed in a three-necked round-bottom flask (condenser / thermometer / dropping funnel) and heated at 75°C until the mixture becomes a clear solution. Pt catalyst (15 ppm) is added, followed by dropwise addition of M... H D n M H (Amount calculated based on target n in ABn). The reaction was monitored by 1H-NMR, and vinyltrimethoxysilane (0.02 equivalents) was added dropwise via a dropping funnel after the reaction was complete (no allyl peak). The reaction was quenched by charcoal upon completion (disappearance of the hydride peak in 1H-NMR). The product was obtained by removing toluene from the filtrate via a rotary evaporator. The product was obtained in liquid form in a yield of approximately >80%. The material was characterized by 1H-NMR.

[0104] The crosslinking agent is selected from alkoxysilicates or alkoxysilanes.

[0105] The condensation-curing organosilicon-imide base polymers used in the examples may vary in concentration of low volatiles or smaller cyclic compounds.

[0106] Pour the composition into a 145mm diameter container. 2 Place it in a 0.15mm Teflon mold and keep it at room temperature for 24 hours to fully cure.

[0107] Thermal stability: Thermal degradation was studied using a TGA instrument, TA TGA Q5000, in a nitrogen or air atmosphere at a heating rate of 10 °C / min up to a temperature of 1000 °C.

[0108] Table 1

[0109]

[0110]

[0111] Table 2

[0112]

[0113] As shown in Tables 1 and 2, the condensation-curing adhesive compositions of the present invention, which contain siloxane-imide as a base polymer, provide good thermal stability compared to those using known base polymers.

[0114] The above description includes examples from this specification. Of course, for the purposes of describing this specification, it is impossible to describe every conceivable combination of components or methods, but those skilled in the art will recognize that many further combinations and arrangements are possible. Therefore, this specification is intended to cover all such changes, modifications, and variations that fall within the spirit and scope of the appended claims. Furthermore, with regard to the extent to which the term "comprising" is used in the specific embodiments or claims, such a term is intended to be inclusive in a manner similar to the term "including," as "including" is interpreted when used as a transitional word in a claim.

[0115] The foregoing description identifies various non-limiting embodiments of aromatic organosilicon compounds and curable compositions comprising such compounds. Modifications can be made by those skilled in the art, as well as those who may make and use the invention. The disclosed embodiments are for illustrative purposes only and are not intended to limit the scope of the invention or the subject matter set forth in the claims.

Claims

1. A condensation-curing composition comprising: (a) an organosilicon-imide base polymer; (b) a crosslinking agent comprising at least two groups reactive with condensation groups in the organosilicon-imide polymer; (c) a condensation-curing catalyst; and (d) optionally, an additive, wherein the organosilicon-imide base polymer (a) is selected from compounds of formula (I): (I) Where R 1 Selected from C5-C20 aryl groups, polycyclic aryl groups containing two or more C5-C20 aryl groups, wherein R 1 It may be unsubstituted or substituted with C1-C6 alkyl, halogen, haloalkyl, hydroxy and / or C1-C5 alkoxy groups; C 1 It can be selected from C1 to C5 alkyl, C5-C20 aryl, C7-C16 arylalkyl or C7-C16 alkylaryl; R 2 R 3 and R 4 They can be the same or different, and can be selected from C1-C3 alkyl or phenyl; R 5 They can be the same or different, and can be selected from C1-C30 alkyl, C1-C30 alkoxy, C1-C30 acyloxy or C1-C30 ketoxime groups; m is an integer between 1 and 30; and n is an integer between 1 and 200.

2. The condensation-curing composition according to claim 1, wherein R 1 It is selected from benzene, naphthalene, benzophenone, biphenyl, diphenylalkanes, diphenyl ethers, isopropylidene diphenylphenoxy, diphenyl sulfone, diphenyl sulfide, norcamphenyl and hexafluoromethylbiphenyl.

3. The condensation-curing composition according to claim 1, wherein R 1 It is benzene.

4. The condensation-curing composition according to any one of claims 1-3, comprising 40% to 95% by weight of the organosilicon-imide base polymer (a) based on the total weight parts of the condensation-curing composition.

5. The condensation-curing composition according to any one of claims 1-3, wherein the organosilicon-imide base polymer (a) is present in an amount of 50% to 91% by weight, based on the total weight parts of the condensation-curing composition.

6. The condensation-curing composition according to any one of claims 1-3, wherein the crosslinking agent (b) is selected from alkoxysilanes, alkoxysilicates, alkoxysiloxanes, oxime silanes, oxime siloxanes, alkenoxysilanes, alkenoxysiloxanes, aminosilanes, carboxylsilanes, carboxylsiloxanes, alkylamide silanes, alkylamide siloxanes, arylamide silanes, arylamide siloxanes, alkoxyaminosilanes, alkylarylamide siloxanes, alkoxycarbamate silanes, alkoxycarbamate siloxanes, or combinations of two or more thereof.

7. The condensation-curing composition according to claim 6, wherein the crosslinking agent (b) is selected from tetraethyl orthosilicate (TEOS), methyltrimethoxysilane (MTMS), or a combination thereof.

8. The condensation-curing composition according to any one of claims 1-3, comprising 0.5 to 50 parts of the condensation-curing organo-based polysiloxane crosslinking agent (b) based on the total weight parts of the condensation-curing composition.

9. The condensation-curing composition according to any one of claims 1-3, comprising 5 to 10 parts of the condensation-curing organo-based polysiloxane crosslinking agent (b) based on the total weight parts of the condensation-curing composition.

10. The condensation-curing composition according to any one of claims 1-3, wherein the catalyst (c) is selected from (i) a metal or organometallic catalyst comprising a metal selected from the group consisting of Ca, Ce, Bi, Fe, Mo, Mn, Pb, Ti, V, Zn, Sn and Y, or (ii) a non-tin catalyst comprising a combination of a carboxylic acid component, an amino-containing silane or a mixture of amino-containing silanes, and optionally an amino-containing siloxane component.

11. The condensation-curing composition according to claim 10, wherein the organometallic catalyst is dibutyltin dilaurate.

12. The condensation-curing composition according to any one of claims 1-3, comprising 0.01 to 5 parts of the catalyst (c) based on 100 parts by weight of the condensation-curing composition.

13. The condensation-curing composition according to any one of claims 1-3, wherein the additive (d) is selected from fillers, pigments, lubricants, viscosity modifiers, antioxidants, light stabilizers, heat stabilizers, flame retardants, inhibitors, adhesion promoters, or combinations of two or more thereof.

14. The condensation-curing composition according to claim 13, wherein the additive (d) is a filler selected from the following: SiO2, TiO2, MgO, ZnO, CaCO3, CeO2, Fe2O3, SiC, clay materials, graphene oxide, boron oxide, BN, carbon nanotubes, zirconium oxide, fly ash, Zr(OEt)4, Ti(OEt)4, polyimide, polybenzimidazole, polyamide-imide, polyBPA sulfone, siloxane-polyimide, siloxane-benzimidazole, siloxane-polysulfone in powder form, or a combination of two or more thereof.

15. The condensation-curing composition according to claim 14, wherein the filler is Fe2O3.

16. The condensation-curing composition according to claim 14 or 15, comprising 0 to 50 parts by weight of filler, based on 100 total parts by weight of the condensation-curing composition.

17. The condensation-curing composition according to claim 14 or 15, comprising 10 to 40 parts by weight of filler, based on 100 total parts by weight of the condensation-curing composition.

18. A cured organosilicon-imide material formed from a condensation-curing composition according to any one of claims 1-17.

19. The cured organosilicon-imide material according to claim 18, when measured by thermogravimetric analysis, exhibits thermal degradation at 400°C to 600°C.

20. The cured material according to claim 18 or 19, wherein the cured silicone-imide material is used on or as part of articles in aerospace equipment, electronic equipment, electronic components, motor vehicles, insulations, coatings, or solvent-resistant films.

21. An article comprising a substrate, wherein the condensation-curing composition according to any one of claims 1-17 is applied to or adhered to the surface of the substrate.

22. The article of claim 21, wherein the substrate comprises a material selected from: plastic material, ceramic, glass, rubber material, filled metal, metal alloy, metallized plastic, coated or painted metal, or a combination of two or more thereof.

23. The article of claim 21, wherein the base material is selected from acrylic polymers, polyesters, polyamides, polyimides, acrylonitrile-styrene copolymers, styrene-acrylonitrile-butadiene terpolymers, polyvinyl chloride, polyethylene, polycarbonate, copolycarbonate, or combinations of two or more thereof.

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