UV-moisture dual-curing silicone adhesive as well as preparation method and application thereof

Abstract

The invention provides a UV-moisture dual-curing silicone adhesive as well as a preparation method and application thereof, and belongs to the technical field of sealants. The UV-moisture dual-curing silicone adhesive is prepared from the following components in parts by weight: 50 to 100 parts of vinyl alkoxy terminated polysiloxane, 10 to 50 parts of alkoxy terminated mercaptopropyl modified polysiloxane, 5 to 10 parts of white carbon black, 2 to 6 parts of a cross-linking agent, 1 to 4 parts of a silane coupling agent, 1 to 5 parts of a photoinitiator, 1 to 4 parts of a photosensitizer, 5 to 14 parts of a photoacid generator and 1 to 5 parts of urea peroxide. The silicone adhesive has excellent storage stability and deep curing speed.

Description

Technical Field

[0001] This application relates to the field of sealant technology, specifically to a UV-moisture dual-curing silicone sealant, its preparation method, and its application. Background Technology

[0002] UV-moisture dual-curing silicone adhesive is an innovative silicone adhesive that combines two curing mechanisms (UV curing and moisture curing). It aims to overcome the limitations of traditional single-curing methods in specific application scenarios, providing higher production efficiency and a wider range of application possibilities.

[0003] Moisture curing of silicone sealants involves the hydrolysis of crosslinking agents or end-capping agents (107) and the condensation of silanols. Adding catalysts such as organotin and organotitanium compounds to the formulation can significantly increase the curing speed. However, when the silicone sealant is not thoroughly dehydrated during production or when the packaging is not properly sealed, the sealant can react with water from the environment or residual water from the production process under the action of a catalyst, resulting in thickening or skinning, thus shortening its shelf life. To address this issue, patent CN117987080A discloses an in-situ enhanced UV-moisture dual-curing silicone sealant, its preparation method, and its applications. This sealant uses UV light to induce alkali production during UV curing, catalyzing moisture curing without the need for organotin or other organometallic catalysts. Even when stored in a high-temperature, high-humidity environment for a certain period, it does not thicken or form a skin, exhibiting excellent storage stability. However, due to the lack of organometallic catalysts, its moisture curing speed is insufficient to meet the requirements of certain applications. Summary of the Invention

[0004] The purpose of this application is to overcome the shortcomings of the prior art and provide a UV-moisture dual-curing silicone adhesive, its preparation method and application.

[0005] To achieve the above objectives, the technical solution adopted in this application is as follows: In the first aspect, a UV-moisture dual-curing silicone adhesive is provided, comprising the following components in parts by weight: 50-100 parts of vinylalkoxy-terminated polysiloxane, 10-50 parts of alkoxy-terminated mercaptopropyl-modified polysiloxane, 5-10 parts of silica, 2-6 parts of crosslinking agent, 1-4 parts of silane coupling agent, 1-5 parts of photoinitiator, 1-4 parts of photosensitizer, 5-14 parts of photoacid generator, and 1-5 parts of urea peroxide.

[0006] In some embodiments, the UV-moisture dual-curing silicone sealant comprises the following components in parts by weight: 70-90 parts vinylalkoxy-terminated polysiloxane, 20-30 parts alkoxy-terminated mercaptopropyl-modified polysiloxane, 5-8 parts silica, 2-3 parts silane coupling agent, 2-4 parts photoinitiator, 2-3 parts photosensitizer, 6-10 parts photoacid generator, and 2-5 parts urea peroxide.

[0007] In some embodiments, the photoacid-generating agent includes at least one of triphenylthionium trifluoroacetate, triphenylthionium p-toluenesulfonate, triphenylthionium camphorsulfonate, triphenylthionium perfluorobutylsulfonate, triphenylthionium nonafluorobutylsulfonate, triphenylthionium-1-butanesulfonate, triphenylthionium-1-naphthalenesulfonate, triphenylthionium-2-naphthalenesulfonate, and triphenylthionium-4-tert-butylbenzenesulfonate.

[0008] In some embodiments, the vinylalkoxy-terminated polysiloxane includes at least one of vinyldimethoxy-terminated polydimethylsiloxane, vinyldimethoxy-terminated methylphenyl-modified polydimethylsiloxane, vinyldimethoxy-terminated diphenyl-modified polydimethylsiloxane, vinyldiethoxy-terminated polydimethylsiloxane, vinyldiethoxy-terminated methylphenyl-modified polydimethylsiloxane, and vinyldiethoxy-terminated diphenyl-modified polydimethylsiloxane.

[0009] In some embodiments, the alkoxy-terminated mercaptopropyl modified polysiloxane includes methyldimethoxy-terminated mercaptopropylmethyl modified polydimethylsiloxane, methyldimethoxy-terminated mercaptopropylmethyl-methylphenyl modified polydimethylsiloxane, methyldimethoxy-terminated mercaptopropylmethyl-diphenyl modified polydimethylsiloxane, methyldiethoxy-terminated mercaptopropylmethyl-diphenyl modified polydimethylsiloxane, methyldiethoxy-terminated mercaptopropylmethyl-diphenyl modified polydimethylsiloxane, and methyldiethoxy-terminated mercaptopropylmethyl-diphenyl... The polydimethylsiloxane is modified from at least one of the following: ethyl dimethoxy-terminated mercaptopropyl methyl-modified polydimethylsiloxane, ethyl dimethoxy-terminated mercaptopropyl methyl-methylphenyl-modified polydimethylsiloxane, ethyl dimethoxy-terminated mercaptopropyl methyl-diphenyl-modified polydimethylsiloxane, ethyl diethoxy-terminated mercaptopropyl methyl-modified polydimethylsiloxane, ethyl diethoxy-terminated mercaptopropyl methyl-methylphenyl-modified polydimethylsiloxane, and ethyl diethoxy-terminated mercaptopropyl methyl-diphenyl-modified polydimethylsiloxane.

[0010] In some embodiments, the crosslinking agent includes at least one of methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-octyltrimethoxysilane, n-octyltriethoxysilane, n-dodecyltrimethoxysilane, n-dodecyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 1,2-bis(trimethoxy)silylethane, 1,2-bis(triethoxy)silylethane, polymethyltriethoxysilane, methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate, isopropyl orthosilicate, and butyl orthosilicate.

[0011] In some embodiments, the silane coupling agent includes at least one selected from γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminoethylaminopropyltrimethoxysilane, γ-aminoethylaminopropyltriethoxysilane, γ-diethylenetriaminopropyltrimethoxysilane, p-aminophenyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-n-butyl-3-aminopropyltrimethoxysilane, bis[3-(trimethoxysilane)propyl]amine, bis[3-(triethoxysilane)propyl]amine, γ-glycidyl etheroxypropyltrimethoxysilane, γ-glycidyl etheroxypropyltriethoxysilane, 2-(3,4-epoxycyclohexane)ethyltrimethoxysilane, and 2-(3,4-epoxycyclohexane)ethyltriethoxysilane.

[0012] In some embodiments, the silica includes at least one of hydrophobic precipitated silica, hydrophilic precipitated silica, hydrophobic fumed silica, and hydrophilic fumed silica.

[0013] In some embodiments, the photoinitiator includes at least one selected from benzoin dimethyl ether, 1-hydroxycyclohexylphenyl ketone, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methyl, 2-hydroxy-4-(2-hydroxyethoxy)-2-methylphenylpropanone, and 2-phenylbenzyl-2-dimethylamine-1-(4-morpholinobenzylphenyl)butanone.

[0014] In some embodiments, the photosensitizer includes at least one selected from isopropylthioxanthonone, 2-chlorothioxanthonone, 1-chloro-4-propoxythioxanthonone, and 2,4-diethylthioxanthonone.

[0015] Secondly, a method for preparing the aforementioned UV-moisture dual-curing silicone adhesive is provided, comprising the following steps: Vinylalkoxy-terminated polysiloxane and alkoxy-terminated mercaptopropyl-modified polysiloxane were mixed evenly and dehydrated under reduced pressure at 60–100°C for 1–2 hours. After dehydration, the mixture was cooled to room temperature, and then a crosslinking agent was added and mixed evenly. Next, silica was added and mixed evenly. Then, coupling agent, photoinitiator, photosensitizer, photoacid generator and urea peroxide were added under light-protected conditions and mixed evenly to obtain UV-moisture dual-curing silicone sealant.

[0016] Thirdly, the application of the aforementioned UV-moisture dual-curing silicone sealant is provided, including: bonding and sealing of electronic and electrical appliances, bonding and sealing of photovoltaic products, bonding and sealing of mechanical equipment, anti-corrosion sealing of oil pipelines, bonding and sealing of acrylic products, or bonding and sealing of building curtain walls.

[0017] Compared with existing technologies, the beneficial effects of this application are as follows: By combining the raw materials of this application according to the specific weight proportions mentioned above, the resulting silicone sealant system contains vinyl alkoxy-terminated polysiloxane and alkoxy-terminated mercaptopropyl-modified polysiloxane. UV light irradiation induces a photoinitiator to generate free radicals, triggering a mercapto-alkene click reaction for curing. Simultaneously with UV curing, UV light induces the photoacid generator to decompose, producing acidic substances. These acidic substances can catalyze the hydrolysis and condensation of alkoxy groups for moisture curing, and also catalyze the decomposition of urea peroxide to produce water, promoting moisture curing. This improves the storage stability and deep curing speed of the UV-moisture dual-curing silicone sealant. The UV-moisture dual-curing silicone sealant of this application, without containing organometallic catalysts, avoids the problem of coexistence between mercapto groups and catalysts such as organometallic gold and tin in mercapto-alkene crosslinking systems. This prevents damage to devices bonded or coated with silicone sealant, and has a wider range of application prospects. Detailed Implementation

[0018] To facilitate understanding of this application, a more complete description will be provided below. However, this application can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a more thorough and complete understanding of the disclosure of this application.

[0019] As used in this article: "Prepared from" is synonymous with "comprising". The terms "comprising", "including", "having", "containing", or any other variations thereof as used herein are intended to cover non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that includes the listed elements is not necessarily limited to those elements, but may include other elements not expressly listed or elements inherent to such composition, step, method, article, or apparatus.

[0020] The conjunction "composed of..." excludes any unspecified elements, steps, or components. If used in a claim, this phrase makes the claim closed, excluding materials other than those described, except for associated conventional impurities. When the phrase "composed of..." appears in a clause of the body of a claim rather than immediately following it, it limits only the elements described in that clause; other elements are not excluded from the claim as a whole.

[0021] When a quantity, concentration, or other value or parameter is expressed as a range, a preferred range, or a range defined by a series of upper and lower preferred values, this should be understood as specifically disclosing all ranges formed by any pair of any upper or preferred value with any lower or preferred value, regardless of whether the range is disclosed individually. For example, when the range “1-5” is disclosed, the described range should be interpreted as including ranges “1-4”, “1-3”, “1-2”, “1-2 and 4-5”, “1-3 and 5”, etc. When numerical ranges are described herein, unless otherwise stated, the range is intended to include its endpoints and all integers and fractions within that range.

[0022] In these embodiments, unless otherwise specified, the portions and percentages are all by weight.

[0023] "Parts by mass" refers to the basic unit of measurement that expresses the mass ratio of multiple components. One part can represent any unit mass, such as 1g or 2.689g. If we say that component A has 'a' parts by mass and component B has 'b' parts by mass, it means that the mass ratio of component A to component B is a:b. It is important to understand that, unlike mass percentage content, the sum of the mass parts of all components is not limited to 100 parts.

[0024] "And / or" is used to indicate that one or both of the described situations may occur, for example, A and / or B includes (A and B) and (A or B).

[0025] In a first aspect, a UV-moisture dual-curing silicone adhesive is provided, comprising the following components in parts by weight: 50-100 parts of vinylalkoxy-terminated polysiloxane, 10-50 parts of alkoxy-terminated mercaptopropyl-modified polysiloxane, 5-10 parts of silica, 2-6 parts of crosslinking agent, 1-4 parts of silane coupling agent, 1-5 parts of photoinitiator, 1-4 parts of photosensitizer, 5-14 parts of photoacid generator, and 1-5 parts of urea peroxide.

[0026] The raw materials of this application are combined according to the specific weight parts mentioned above. In the resulting silicone sealant system, vinyl alkoxy-terminated polysiloxane and alkoxy-terminated mercaptopropyl-modified polysiloxane are cured by UV light irradiation, which induces a photoinitiator to generate free radicals and initiates a mercapto-alkene click reaction. Simultaneously with UV curing, UV light induces the photoacid generator to decompose and produce acidic substances. These acidic substances can catalyze the hydrolysis and condensation of alkoxy groups for moisture curing, and can also catalyze the decomposition of urea peroxide to produce water, promoting moisture curing. This improves the storage stability and deep curing speed of the UV-moisture dual-curing silicone sealant. The UV-moisture dual-curing silicone sealant of this application does not contain organometallic catalysts, avoiding the problem of coexistence between mercapto groups and organometallic catalysts such as gold and tin in mercapto-alkene crosslinking systems. This prevents damage to devices bonded or coated with silicone sealant and has a wider range of application prospects.

[0027] In this application, controlling the weight of the photoacid generator to be 5-14 parts and the weight of urea peroxide to be 1-5 parts can effectively improve the deep curing speed of UV-moisture dual-curing silicone adhesive. If the weight of the photoacid generator and / or urea peroxide is too low, there will be less acidic substances induced by UV light, resulting in less water produced by alkoxy hydrolysis and / or urea peroxide decomposition, leading to a decrease in the deep curing speed and adhesive strength of the UV-moisture dual-curing silicone adhesive. If the weight of the photoacid generator and / or urea peroxide is too high, there will be more acidic substances induced by UV light, resulting in excessive water produced by alkoxy hydrolysis and / or urea peroxide decomposition, leading to an excessively fast moisture curing speed of the UV-moisture dual-curing silicone adhesive and insufficient wetting time for the substrate, resulting in a decrease in the adhesive performance of the UV-moisture dual-curing silicone adhesive.

[0028] The photosensitizer in this application can sensitize the photoinitiator, promoting photocuring based on the mercapto-olefin click reaction. By controlling the amount of photosensitizer within the range of this invention, the deep curing speed of UV-moisture dual-curing silicone adhesive is effectively improved. If the amount added is too small, the sensitization effect on the system is low; if the amount added is too large, it will lead to a decrease in the conversion rate of the mercapto-olefin click reaction and a decrease in the deep curing speed of the UV-moisture dual-curing silicone adhesive, which is not conducive to the application of UV-moisture dual-curing silicone adhesive in certain fields.

[0029] In this application, silica can form a reinforced filler network with polysiloxane, which can improve the tensile strength and adhesive strength of UV-moisture dual-curing silicone adhesive.

[0030] Specifically, the vinylalkoxy-terminated polysiloxane can be in the range of 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts, 90 parts, 95 parts, 100 parts or any combination thereof by weight.

[0031] Specifically, the weight parts of the alkoxy-terminated mercaptopropyl modified polysiloxane can be in the range of 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, or any combination of both.

[0032] Specifically, the weight parts of silica can be a range of 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts, 8.5 parts, 9 parts, 9.5 parts, 10 parts or any combination of two of these.

[0033] Specifically, the weight parts of the crosslinking agent can be one or any combination of two of the following: 2 parts, 2.3 parts, 2.5 parts, 2.8 parts, 3 parts, 3.2 parts, 3.5 parts, 3.7 parts, 4 parts, 4.2 parts, 4.5 parts, 4.7 parts, 5 parts, 5.3 parts, 5.5 parts, 5.8 parts, and 6 parts.

[0034] Specifically, the weight parts of the silane coupling agent can be one or any combination of two of the following: 1 part, 1.2 parts, 1.5 parts, 1.7 parts, 2 parts, 2.3 parts, 2.5 parts, 2.8 parts, 3 parts, 3.2 parts, 3.5 parts, 3.8 parts, and 4 parts.

[0035] Specifically, the weight parts of the photoinitiator can be one or any combination of 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, or any combination of two of these values.

[0036] Specifically, the weight parts of the photosensitizer can be one or any combination of two of the following: 1 part, 1.2 parts, 1.5 parts, 1.7 parts, 2 parts, 2.3 parts, 2.5 parts, 2.8 parts, 3 parts, 3.2 parts, 3.5 parts, 3.8 parts, and 4 parts.

[0037] Specifically, the weight parts of the photoacid-generating agent can be one or any combination of 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, and 14 parts.

[0038] Specifically, the weight parts of urea peroxide can be one or any combination of two of the following: 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, and 5 parts.

[0039] In some embodiments, the UV-moisture dual-curing silicone sealant comprises the following components in parts by weight: 60-80 parts of vinylalkoxy-terminated polysiloxane, 20-40 parts of alkoxy-terminated mercaptopropyl-modified polysiloxane, 6-8 parts of silica, 3-5 parts of crosslinking agent, 1-3 parts of silane coupling agent, 2-4 parts of photoinitiator, 2-3 parts of photosensitizer, 8-12 parts of photoacid generator, and 1-3 parts of urea peroxide.

[0040] The amount of each raw material in the UV-moisture dual-curing silicone sealant of this application is within the above range, resulting in higher compatibility and compatibility of the silicone sealant system, which is beneficial to further improve the overall performance of the UV-moisture dual-curing silicone sealant.

[0041] In some embodiments, the photoacid-generating agent includes at least one of triphenylthionium trifluoroacetate, triphenylthionium p-toluenesulfonate, triphenylthionium camphorsulfonate, triphenylthionium perfluorobutylsulfonate, triphenylthionium nonafluorobutylsulfonate, triphenylthionium-1-butanesulfonate, triphenylthionium-1-naphthalenesulfonate, triphenylthionium-2-naphthalenesulfonate, and triphenylthionium-4-tert-butylbenzenesulfonate.

[0042] In some embodiments, the vinylalkoxy-terminated polysiloxane includes at least one of vinyldimethoxy-terminated polydimethylsiloxane, vinyldimethoxy-terminated methylphenyl-modified polydimethylsiloxane, vinyldimethoxy-terminated diphenyl-modified polydimethylsiloxane, vinyldiethoxy-terminated polydimethylsiloxane, vinyldiethoxy-terminated methylphenyl-modified polydimethylsiloxane, and vinyldiethoxy-terminated diphenyl-modified polydimethylsiloxane.

[0043] In some embodiments, the vinylalkoxy-terminated polysiloxane has a viscosity of 20,000 to 100,000 mPa·s at 25°C; for example, it can be a range of one or any two of 20,000 mPa·s, 30,000 mPa·s, 40,000 mPa·s, 50,000 mPa·s, 60,000 mPa·s, 70,000 mPa·s, 80,000 mPa·s, 90,000 mPa·s, and 100,000 mPa·s.

[0044] In some embodiments, the alkoxy-terminated mercaptopropyl modified polysiloxane includes methyldimethoxy-terminated mercaptopropylmethyl modified polydimethylsiloxane, methyldimethoxy-terminated mercaptopropylmethyl-methylphenyl modified polydimethylsiloxane, methyldimethoxy-terminated mercaptopropylmethyl-diphenyl modified polydimethylsiloxane, methyldiethoxy-terminated mercaptopropylmethyl-diphenyl modified polydimethylsiloxane, methyldiethoxy-terminated mercaptopropylmethyl-diphenyl modified polydimethylsiloxane, and methyldiethoxy-terminated mercaptopropylmethyl-diphenyl... The polydimethylsiloxane is modified from at least one of the following: ethyl dimethoxy-terminated mercaptopropyl methyl-modified polydimethylsiloxane, ethyl dimethoxy-terminated mercaptopropyl methyl-methylphenyl-modified polydimethylsiloxane, ethyl dimethoxy-terminated mercaptopropyl methyl-diphenyl-modified polydimethylsiloxane, ethyl diethoxy-terminated mercaptopropyl methyl-modified polydimethylsiloxane, ethyl diethoxy-terminated mercaptopropyl methyl-methylphenyl-modified polydimethylsiloxane, and ethyl diethoxy-terminated mercaptopropyl methyl-diphenyl-modified polydimethylsiloxane.

[0045] In some embodiments, the alkoxy-terminated mercaptopropyl modified polysiloxane has a viscosity of 5000~80000 mPa·s at 25°C; for example, it can be a range of one or any two of 5000 mPa·s, 10000 mPa·s, 20000 mPa·s, 30000 mPa·s, 40000 mPa·s, 50000 mPa·s, 60000 mPa·s, 70000 mPa·s, and 80000 mPa·s.

[0046] In some embodiments, the crosslinking agent includes at least one of methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-octyltrimethoxysilane, n-octyltriethoxysilane, n-dodecyltrimethoxysilane, n-dodecyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 1,2-bis(trimethoxy)silylethane, 1,2-bis(triethoxy)silylethane, polymethyltriethoxysilane, methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate, isopropyl orthosilicate, and butyl orthosilicate.

[0047] In some embodiments, the silane coupling agent includes at least one selected from γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminoethylaminopropyltrimethoxysilane, γ-aminoethylaminopropyltriethoxysilane, γ-diethylenetriaminopropyltrimethoxysilane, p-aminophenyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-n-butyl-3-aminopropyltrimethoxysilane, bis[3-(trimethoxysilane)propyl]amine, bis[3-(triethoxysilane)propyl]amine, γ-glycidyl etheroxypropyltrimethoxysilane, γ-glycidyl etheroxypropyltriethoxysilane, 2-(3,4-epoxycyclohexane)ethyltrimethoxysilane, and 2-(3,4-epoxycyclohexane)ethyltriethoxysilane.

[0048] In some embodiments, the silica includes at least one of hydrophobic precipitated silica, hydrophilic precipitated silica, hydrophobic fumed silica, and hydrophilic fumed silica.

[0049] In some embodiments, the photoinitiator includes at least one selected from benzoin dimethyl ether, 1-hydroxycyclohexylphenyl ketone, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methyl, 2-hydroxy-4-(2-hydroxyethoxy)-2-methylphenylpropanone, and 2-phenylbenzyl-2-dimethylamine-1-(4-morpholinobenzylphenyl)butanone.

[0050] In some embodiments, the photosensitizer includes at least one selected from isopropylthioxanthonone, 2-chlorothioxanthonone, 1-chloro-4-propoxythioxanthonone, and 2,4-diethylthioxanthonone.

[0051] Secondly, a method for preparing the aforementioned UV-moisture dual-curing silicone adhesive is provided, comprising the following steps: Vinylalkoxy-terminated polysiloxane and alkoxy-terminated mercaptopropyl-modified polysiloxane were mixed evenly and dehydrated under reduced pressure at 60–100°C for 1–2 hours. After dehydration, the mixture was cooled to room temperature, and then a crosslinking agent was added and mixed evenly. Next, silica was added and mixed evenly. Then, coupling agent, photoinitiator, photosensitizer, photoacid generator and urea peroxide were added under light-protected conditions and mixed evenly to obtain UV-moisture dual-curing silicone sealant.

[0052] Thirdly, the application of the aforementioned UV-moisture dual-curing silicone sealant is provided, including: bonding and sealing of electronic and electrical appliances, bonding and sealing of photovoltaic products, bonding and sealing of mechanical equipment, anti-corrosion sealing of oil pipelines, bonding and sealing of acrylic products, or bonding and sealing of building curtain walls.

[0053] In this application, there are no particular restrictions on the specific dispersion and mixing methods.

[0054] Unless otherwise specified, all components, raw materials, or instruments used in the embodiments and comparative examples of this invention are commercially available, and the components and raw materials used in each parallel experiment are the same.

[0055] In the examples and comparative examples, the vinyl dimethoxy-terminated polydimethylsiloxane with a viscosity of 80000 mPa·s was sourced from Shanghai Huiyan New Materials Co., Ltd., VTM series.

[0056] In the examples and comparative examples, the vinyl dimethoxy-terminated polydimethylsiloxane with a viscosity of 50000 mPa·s was sourced from Shanghai Huiyan New Materials Co., Ltd., VTM series.

[0057] The preparation method of methyldimethoxy-terminated mercaptopropylmethyl modified polydimethylsiloxane with a viscosity of 50000 mPa·s in the examples and comparative examples is as follows: 1.46 g of mercaptopropylmethyldimethoxysilane, 300 g of octamethylcyclotetrasiloxane, 0.3 g of deionized water, and 3.15 g of trifluoromethanesulfonic acid were added to a flask equipped with a condenser. The mixture was stirred at 65°C for 2 h, then heated to 90°C and stirred for 6 h. Finally, the product was washed with water until neutral and low-boiling substances were removed under reduced pressure to obtain the initial product. Add 250g of the initial product, 2.5g of methyltrimethoxysilane, and 0.25g of tetramethylammonium hydroxide alkali gel to a dry flask equipped with a condenser. Under sealed and nitrogen protection, heat to 60℃ and stir for 1h. Then heat to 90℃ and reduce pressure to -0.08~-0.1MPa and stir for 2h to decompose the catalyst and remove low-boiling substances. Finally, cool the reactants to room temperature to obtain methyldimethoxy-terminated mercaptopropylmethyl modified polydimethylsiloxane.

[0058] Example 1 This embodiment provides a UV-moisture dual-curing silicone adhesive, comprising the following components in parts by weight: 80 parts of vinyl dimethoxy-terminated polydimethylsiloxane with a viscosity of 80000 mPa·s, 40 parts of methyl dimethoxy-terminated mercaptopropylmethyl-modified polydimethylsiloxane with a viscosity of 50000 mPa·s, 6 parts of hydrophobic fumed silica, 4 parts of methyltriethoxysilane, 1 part of γ-aminopropyltriethoxysilane, 0.5 parts of γ-glycidyl etheroxypropyltrimethoxysilane, 3 parts of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2 parts of isopropylthioxanthraquinone, 8 parts of triphenylthionium p-toluenesulfonate, and 1 part of urea peroxide.

[0059] The preparation method of the UV-moisture dual-curing silicone adhesive in this embodiment includes the following steps: Vinylalkoxy-terminated polysiloxane and alkoxy-terminated mercaptopropyl-modified polysiloxane were mixed evenly and dehydrated under reduced pressure at 80°C for 1 hour. After dehydration, the mixture was cooled to room temperature, and then a crosslinking agent was added and mixed evenly. Next, silica was added and mixed evenly. Then, coupling agent, photoinitiator, photosensitizer, photoacid generator and urea peroxide were added under light-protected conditions and mixed evenly to obtain UV-moisture dual-curing silicone sealant.

[0060] Example 2 This embodiment provides a UV-moisture dual-curing silicone adhesive, comprising the following components in parts by weight: 60 parts of vinyl dimethoxy-terminated polydimethylsiloxane with a viscosity of 80000 mPa·s, 20 parts of methyl dimethoxy-terminated mercaptopropylmethyl-modified polydimethylsiloxane with a viscosity of 50000 mPa·s, 8 parts of hydrophobic fumed silica, 3 parts of methyltriethoxysilane, 2 parts of γ-aminopropyltriethoxysilane, 1 part of γ-glycidyl etheroxypropyltrimethoxysilane, 2 parts of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 3 parts of isopropylthioxanthraquinone, 8 parts of triphenylthionium p-toluenesulfonate, and 1 part of urea peroxide.

[0061] The preparation method of the UV-moisture dual-curing silicone sealant in this embodiment is the same as that in the previous embodiment.

[0062] Example 3 This embodiment provides a UV-moisture dual-curing silicone adhesive, comprising the following components in parts by weight: 100 parts of vinyl dimethoxy-terminated polydimethylsiloxane with a viscosity of 80000 mPa·s, 50 parts of methyl dimethoxy-terminated mercaptopropylmethyl-modified polydimethylsiloxane with a viscosity of 50000 mPa·s, 5 parts of hydrophobic fumed silica, 6 parts of methyltriethoxysilane, 0.7 parts of γ-aminopropyltriethoxysilane, 0.3 parts of γ-glycidyl etheroxypropyltrimethoxysilane, 5 parts of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 4 parts of isopropylthioxanthraquinone, 8 parts of triphenylthionium p-toluenesulfonate, and 1 part of urea peroxide.

[0063] The preparation method of the UV-moisture dual-curing silicone sealant in this embodiment is the same as that in the previous embodiment.

[0064] Example 4 This embodiment provides a UV-moisture dual-curing silicone adhesive, comprising the following components in parts by weight: 50 parts of vinyl dimethoxy-terminated polydimethylsiloxane with a viscosity of 80000 mPa·s, 10 parts of methyl dimethoxy-terminated mercaptopropylmethyl-modified polydimethylsiloxane with a viscosity of 50000 mPa·s, 10 parts of hydrophobic fumed silica, 2 parts of methyltriethoxysilane, 2.5 parts of γ-aminopropyltriethoxysilane, 1.5 parts of γ-glycidyl etheroxypropyltrimethoxysilane, 1 part of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1 part of isopropylthioxanthraquinone, 8 parts of triphenylthionium p-toluenesulfonate, and 1 part of urea peroxide.

[0065] The preparation method of the UV-moisture dual-curing silicone sealant in this embodiment is the same as that in the previous embodiment.

[0066] Example 5 This embodiment provides a UV-moisture dual-curing silicone sealant, which differs from the UV-moisture dual-curing silicone sealant of Example 1 in that the weight of triphenylthionium p-toluenesulfonate in this embodiment is 12 parts.

[0067] Example 6 This embodiment provides a UV-moisture dual-curing silicone sealant, which differs from the UV-moisture dual-curing silicone sealant of Example 1 in that the weight of triphenylthionium p-toluenesulfonate in this embodiment is 14 parts.

[0068] Example 7 This embodiment provides a UV-moisture dual-curing silicone sealant, which differs from the UV-moisture dual-curing silicone sealant of Example 1 in that: in this embodiment, the weight of triphenylthionium p-toluenesulfonate is 5 parts.

[0069] Example 8 This embodiment provides a UV-moisture dual-curing silicone sealant, which differs from the UV-moisture dual-curing silicone sealant of Example 1 in that the weight of urea peroxide in this embodiment is 3 parts.

[0070] Example 9 This embodiment provides a UV-moisture dual-curing silicone sealant, which differs from the UV-moisture dual-curing silicone sealant of Example 1 in that the weight of urea peroxide in this embodiment is 5 parts.

[0071] Example 10 This embodiment provides a UV-moisture dual-curing silicone sealant, which differs from the UV-moisture dual-curing silicone sealant of Example 1 in that triphenylthionium p-toluenesulfonate is used instead of triphenylthionium trifluoroacetate.

[0072] Comparative Example 1 This comparative example provides a UV-moisture dual-curing silicone sealant, which differs from the UV-moisture dual-curing silicone sealant of Example 1 in that the weight of triphenylthionium p-toluenesulfonate in this comparative example is 3 parts.

[0073] Comparative Example 2 This comparative example provides a UV-moisture dual-curing silicone sealant, which differs from the UV-moisture dual-curing silicone sealant of Example 1 in that the weight of triphenylthionium p-toluenesulfonate in this comparative example is 16 parts.

[0074] Comparative Example 3 This comparative example provides a UV-moisture dual-curing silicone sealant, which differs from the UV-moisture dual-curing silicone sealant of Example 1 in that the weight of urea peroxide in this comparative example is 0 parts.

[0075] Comparative Example 4 This comparative example provides a UV-moisture dual-curing silicone sealant, which differs from the UV-moisture dual-curing silicone sealant of Example 1 in that the weight of urea peroxide in this comparative example is 7 parts.

[0076] Comparative Example 5 This comparative example provides a UV-moisture dual-curing silicone sealant, which differs from the UV-moisture dual-curing silicone sealant of Example 1 in that urea is used instead of urea peroxide.

[0077] Comparative Example 6 This comparative example provides a UV-moisture dual-curing silicone sealant, which differs from the UV-moisture dual-curing silicone sealant of Example 1 in that it uses tetraethyl orthosilicate instead of hydrophobic fumed silica.

[0078] Comparative Example 7 This comparative example provides a UV-moisture dual-curing silicone adhesive comprising the following components in parts by weight: 80 parts of vinyl dimethoxy-terminated polydimethylsiloxane with a viscosity of 80000 mPa·s, 40 parts of methyl dimethoxy-terminated mercaptopropylmethyl-modified polydimethylsiloxane with a viscosity of 50000 mPa·s, 6 parts of hydrophobic fumed silica, 4 parts of methyltriethoxysilane, 1 part of γ-aminopropyltriethoxysilane, 0.5 parts of γ-glycidyl etheroxypropyltrimethoxysilane, 3 parts of 2-hydroxy-2-methyl-1-phenyl-1-propanone, and 0.2 parts of dibutyltin dilaurate.

[0079] The preparation method of this comparative UV-moisture dual-curing silicone adhesive includes the following steps: Vinylalkoxy-terminated polysiloxane and alkoxy-terminated mercaptopropyl-modified polysiloxane were mixed evenly and dehydrated under reduced pressure at 80°C for 1 hour. After dehydration, the mixture was cooled to room temperature, and then a crosslinking agent was added and mixed evenly. Next, silica was added and mixed evenly. Then, a coupling agent, a photoinitiator, and dibutyltin dilaurate were added under light-protected conditions and mixed evenly to obtain a UV-moisture dual-curing silicone sealant.

[0080] Comparative Example 8 This comparative example provides a UV-moisture dual-curing silicone adhesive, prepared according to the composition and preparation method of the UV-moisture dual-curing silicone adhesive in Example 2 of Patent 2024100369255. The UV-moisture dual-curing silicone adhesive comprises the following components in parts by weight: 75 parts of vinyl dimethoxy-terminated polydimethylsiloxane with a viscosity of 50,000 mPa·s, 30 parts of methyl dimethoxy-terminated mercaptopropylmethyl-modified polydimethylsiloxane with a viscosity of 50,000 mPa·s, 2 parts of γ-aminopropyltriethoxysilane, 70 parts of tetraethyl orthosilicate, 5 parts of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 3 parts of isopropylthioxanthraquinone, and 6 parts of TBDNPG.

[0081] The preparation method of the UV-moisture dual-curing silicone adhesive includes the following steps: The above-mentioned vinyl dimethoxy-terminated polydimethylsiloxane and methyl dimethoxy-terminated mercaptopropylmethyl-modified polydimethylsiloxane were mixed evenly and dehydrated under reduced pressure at 120°C for 1 hour. After dehydration, the mixture was cooled to room temperature. Then, γ-aminopropyltriethoxysilane, tetraethyl orthosilicate, 2-hydroxy-2-methyl-1-phenyl-1-propanone, isopropylthioxanthanone and TBDNPG were added under light-protected conditions and mixed evenly to obtain UV-moisture dual-curing silicone sealant. The structural formula of TBDNPG is shown in equation VIII: .

[0082] The preparation method of TBDNPG is as follows: 0.5 mol of 1,5,7-triazabicyclo[4.4.0]dec-5-ene is dissolved in 50 g of deionized water, and 0.55 mol of N-phenylglycine is dissolved in 100 g of deionized water. While stirring, the aqueous solution of N-phenylglycine is added dropwise to the aqueous solution of 1,5,7-triazabicyclo[4.4.0]dec-5-ene. After the addition is complete, stirring is continued for 1 h. The reaction solution is extracted and distilled under reduced pressure to obtain the compound (TBDNPG) shown in Formula VIII.

[0083] Performance testing UV-moisture dual-curing silicone adhesive 24h curing depth: The silicone adhesive is extruded into a black cap-shaped container with a diameter of 1cm and a depth of 1cm, and then immediately cured by irradiation with a 365nm point light source at a UV light intensity of 10mW·cm. -2 The exposure time was 10 seconds. Then, the sample was placed in an environment with a temperature of (23±2)℃ and a relative humidity of (50±5)% for 24 hours. The silicone sealant was then removed and the surface residue of uncured silicone sealant was washed off with alcohol. The thickness of the cured silicone sealant was measured, and the average value of 5 samples was taken.

[0084] UV-moisture dual-curing silicone adhesive shear strength: Shear strength was tested according to standard GB / T 7124-2008, with glass-to-glass substrate. Irradiation curing was performed using a 365nm conveyor belt curing machine with a UV light intensity of 100mW·cm². -2 The exposure time was 10 seconds, and the samples were placed in an environment with a temperature of (23±2)℃ and a relative humidity of (50±5)% for 7 days before testing.

[0085] Storage stability of UV-moisture dual-curing silicone sealant: Freshly produced, uncured silicone sealant was sealed in a bottle. Consistency was tested according to GB / T 1749-1979 for 2 minutes. An unopened bottle of UV-moisture dual-curing silicone sealant was placed in a 70℃×70%RH constant temperature and humidity chamber for 7 days. Consistency was tested, and the bottle was cut open to observe the curing process.

[0086] The test results are shown in Table 1.

[0087] Table 1 As can be seen from the experimental data in Table 1, the UV-moisture dual-curing silicone adhesive of this application has a curing depth greater than 5 mm and a shear strength greater than 1.8 MPa after 24 hours of moisture curing, indicating that the UV-moisture dual-curing silicone adhesive of this application has good moisture curing depth and bonding performance.

[0088] The experimental data from Examples 1 and Comparative Examples 1-4 show that the lack of photoacid generators or urea peroxide, or the excessive addition of photoacid generators or urea peroxide, makes it difficult for UV-moisture dual-curing silicone adhesives to achieve both moisture curing depth and bonding performance.

[0089] The experimental data from Example 1 and Comparative Example 5 show that replacing urea peroxide with urea in Comparative Example 5 leads to a decrease in the moisture curing depth and bonding performance of the UV-moisture dual-curing silicone adhesive.

[0090] The experimental data from Example 1 and Comparative Example 6 show that when tetraethyl orthosilicate was used to replace hydrophobic fumed silica in Comparative Example 6, the resulting UV-moisture dual-curing silicone adhesive was a non-thixotropic fluid, and the moisture curing depth and bonding performance of the UV-moisture dual-curing silicone adhesive decreased.

[0091] The experimental data from Example 1 and Comparative Example 7 show that the use of an organotin catalyst in Comparative Example 7 not only leads to a decrease in the moisture curing depth and adhesion performance of the UV-moisture dual-curing silicone sealant, but also reduces the storage stability of the UV-moisture dual-curing silicone sealant.

[0092] The UV-moisture dual-curing silicone adhesive of Comparative Example 8 is a non-thixotropic fluid, so no consistency test was performed.

[0093] Finally, it should be noted that the above embodiments are used to illustrate the technical solutions of this application and not to limit the scope of protection of this application. Although this application has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of this application without departing from the substance and scope of the technical solutions of this application.

Claims

1. A UV-moisture dual-curing silicone adhesive, characterized in that, It comprises the following components in parts by weight: 50-100 parts of vinylalkoxy-terminated polysiloxane, 10-50 parts of alkoxy-terminated mercaptopropyl-modified polysiloxane, 5-10 parts of silica, 2-6 parts of crosslinking agent, 1-4 parts of silane coupling agent, 1-5 parts of photoinitiator, 1-4 parts of photosensitizer, 5-14 parts of photoacid generator, and 1-5 parts of urea peroxide.

2. The UV-moisture dual-curing silicone adhesive as described in claim 1, characterized in that, The product comprises the following components in parts by weight: 70-90 parts vinylalkoxy-terminated polysiloxane, 20-30 parts alkoxy-terminated mercaptopropyl-modified polysiloxane, 5-8 parts silica, 2-3 parts silane coupling agent, 2-4 parts photoinitiator, 2-3 parts photosensitizer, 6-10 parts photoacid generator, and 2-5 parts urea peroxide.

3. The UV-moisture dual-curing silicone adhesive as described in claim 1 or 2, characterized in that, The photoacid-generating agent includes at least one of triphenylthionium trifluoroacetate, triphenylthionium p-toluenesulfonate, triphenylthionium camphorsulfonate, triphenylthionium perfluorobutylsulfonate, triphenylthionium nonafluorobutylsulfonate, triphenylthionium-1-butanesulfonate, triphenylthionium-1-naphthalenesulfonate, triphenylthionium-2-naphthalenesulfonate, and triphenylthionium-4-tert-butylbenzenesulfonate.

4. The UV-moisture dual-curing silicone adhesive as described in claim 1 or 2, characterized in that, The vinylalkoxy-terminated polysiloxane includes at least one of vinyl dimethoxy-terminated polydimethylsiloxane, vinyl dimethoxy-terminated methylphenyl-modified polydimethylsiloxane, vinyl dimethoxy-terminated diphenyl-modified polydimethylsiloxane, vinyl diethoxy-terminated polydimethylsiloxane, vinyl diethoxy-terminated methylphenyl-modified polydimethylsiloxane, and vinyl diethoxy-terminated diphenyl-modified polydimethylsiloxane.

5. The UV-moisture dual-curing silicone adhesive as described in claim 1 or 2, characterized in that, The alkoxy-terminated mercaptopropyl modified polysiloxanes include methyl dimethoxy-terminated mercaptopropyl methyl modified polydimethylsiloxane, methyl dimethoxy-terminated mercaptopropyl methyl-methylphenyl modified polydimethylsiloxane, methyl dimethoxy-terminated mercaptopropyl methyl-diphenyl modified polydimethylsiloxane, methyl diethoxy-terminated mercaptopropyl methyl modified polydimethylsiloxane, methyl diethoxy-terminated mercaptopropyl methyl-methylphenyl modified polydimethylsiloxane, and methyl diethoxy-terminated mercaptopropyl methyl-diphenyl modified polydimethylsiloxane. At least one of the following: dimethylsiloxane, ethyl dimethoxy-terminated mercaptopropyl methyl modified polydimethylsiloxane, ethyl dimethoxy-terminated mercaptopropyl methyl-methylphenyl modified polydimethylsiloxane, ethyl dimethoxy-terminated mercaptopropyl methyl-diphenyl modified polydimethylsiloxane, ethyl diethoxy-terminated mercaptopropyl methyl modified polydimethylsiloxane, ethyl diethoxy-terminated mercaptopropyl methyl-methylphenyl modified polydimethylsiloxane, and ethyl diethoxy-terminated mercaptopropyl methyl-diphenyl modified polydimethylsiloxane.

6. The UV-moisture dual-curing silicone adhesive as described in claim 1 or 2, characterized in that, The crosslinking agent includes at least one of methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-octyltrimethoxysilane, n-octyltriethoxysilane, n-dodecyltrimethoxysilane, n-dodecyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 1,2-bis(trimethoxy)silylethane, 1,2-bis(triethoxy)silylethane, polymethyltriethoxysilane, methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate, isopropyl orthosilicate, and butyl orthosilicate.

7. The UV-moisture dual-curing silicone adhesive as described in claim 1 or 2, characterized in that, The silane coupling agent includes at least one of γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminoethylaminopropyltrimethoxysilane, γ-aminoethylaminopropyltriethoxysilane, γ-diethylenetriaminopropyltrimethoxysilane, p-aminophenyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-n-butyl-3-aminopropyltrimethoxysilane, bis[3-(trimethoxysilane)propyl]amine, bis[3-(triethoxysilane)propyl]amine, γ-glycidyl etheroxypropyltrimethoxysilane, γ-glycidyl etheroxypropyltriethoxysilane, 2-(3,4-epoxycyclohexane)ethyltrimethoxysilane, and 2-(3,4-epoxycyclohexane)ethyltriethoxysilane.

8. The UV-moisture dual-curing silicone adhesive as described in claim 1 or 2, characterized in that, Meet at least one of the following: (a) The silica includes at least one of hydrophobic precipitated silica, hydrophilic precipitated silica, hydrophobic fumed silica, and hydrophilic fumed silica; (b) The photoinitiator comprises at least one of benzoin dimethyl ether, 1-hydroxycyclohexylphenyl ketone, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methyl, 2-hydroxy-4-(2-hydroxyethoxy)-2-methylphenylpropanone, and 2-phenylbenzyl-2-dimethylamine-1-(4-morpholinobenzylphenyl)butanone; (c) The photosensitizer includes at least one of isopropylthioxanthonone, 2-chlorothioxanthonone, 1-chloro-4-propoxythioxanthonone, and 2,4-diethylthioxanthonone.

9. A method for preparing a UV-moisture dual-curing silicone adhesive as described in any one of claims 1-9, characterized in that, Includes the following steps: Vinylalkoxy-terminated polysiloxane and alkoxy-terminated mercaptopropyl-modified polysiloxane were mixed evenly and dehydrated under reduced pressure at 60–100°C for 1–2 hours. After dehydration, the mixture was cooled to room temperature, and then a crosslinking agent was added and mixed evenly. Next, silica was added and mixed evenly. Then, coupling agent, photoinitiator, photosensitizer, photoacid generator and urea peroxide were added under light-protected conditions and mixed evenly to obtain UV-moisture dual-curing silicone sealant.

10. The application of the UV-moisture dual-curing silicone sealant as described in any one of claims 1-9, characterized in that, include: Bonding and sealing of electronic and electrical appliances, photovoltaic products, mechanical equipment, oil pipelines, acrylic products, and building curtain walls.

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