Catalytic system, two-component rapid curing dealcoholization condensation type organic silicon adhesive and preparation method thereof

Abstract

The invention relates to the technical field of organic silicon adhesives, and provides a catalytic system, a two-component rapid curing dealcoholization condensation type organic silicon adhesive and a preparation method thereof.The catalytic system comprises a condensation reaction between silanol and a siloxane cross-linking agent and a catalyst composition for increasing the condensation reaction rate, and the catalyst composition comprises 1, 3, 5-trimethyl-1, 3, 5-trimethyl-1, 3, 5-trimethyl-1, 3, 5-trimethyl-1, 3, 5-trimethyl-1, 3, 5-trimethyl-1, 3, 5-trimethyl-1, 3, 5- The invention relates to 2, 4-tribenzyl-1, 2, 4-triazolium chloride and a metal-based catalyst. By constructing the novel catalytic system, the strong electron donating characteristic of the triazolium compound can be fully utilized, the electron density of a metal catalytic center is enhanced, and the electrophilicity of the metal center of the catalytic system is improved, so that the activity of the titanium-tin composite catalytic system is further improved. When the catalyst composition is used in a double-component dealcoholization condensation type organic silicon adhesive, the surface drying time can be remarkably shortened (rapid curing is realized), meanwhile, a compact and uniform cross-linked network is formed by siloxane chain segments, and finally excellent mechanical properties are obtained.

Description

Technical Field

[0001] This invention relates to the field of adhesive technology, and in particular to a catalytic system, a two-component fast-curing de-alcohol condensation type silicone adhesive, and a method for preparing the same. Background Technology

[0002] Silicone adhesives are widely used in electronics, automotive manufacturing, construction engineering, and new energy fields due to their excellent weather resistance, high and low temperature resistance, electrical insulation, and chemical stability. Based on different curing mechanisms, room temperature vulcanizing (RTV) silicone adhesives are mainly classified into deacidification type, deoxime type, and de-alcoholization condensation type. Among them, de-alcoholization condensation type silicone adhesives release small alcohol molecules during curing, offering significant advantages such as non-corrosiveness, low odor, and wide substrate compatibility.

[0003] Two-component condensation-de-alcoholization type silicone rubbers typically consist of two components, A and B, which are mixed in a specific ratio and cured at room temperature through a condensation reaction. Currently, most commercially available two-component silicone adhesives have relatively long surface drying times, significantly reducing bonding efficiency and hindering production. While some adhesives may have short surface drying times and relatively fast curing speeds, their mechanical properties are often inferior. Summary of the Invention

[0004] Research has found that the core reason for the difficulty in simultaneously achieving optimal surface drying time and mechanical properties is largely limited by the existing catalyst system, filler, and coupling agent ratios. However, in the field of two-component alcohol-dehydration condensation type organotin adhesives, dibutyltin dilaurate is the most widely used and technologically mature organotin catalyst. Experiments have shown that simply adjusting the amount of dibutyltin dilaurate is insufficient to significantly increase the curing speed while simultaneously maintaining the adhesive's mechanical properties.

[0005] Based on this, the present invention proposes a catalytic system, a two-component fast-curing de-alcohol condensation type silicone adhesive and its preparation method. By using 1,3,4-tribenzyl-1,2,4-triazolium chloride in combination with a metal-based catalyst, the activity of the catalytic system is further enhanced. While significantly shortening the surface drying time and curing time, the adhesive also ensures that it has excellent mechanical properties.

[0006] To this end, the present invention proposes a catalytic system comprising a condensation reaction between silanol and a siloxane crosslinking agent, and a catalyst composition for enhancing the rate of the condensation reaction, the catalyst composition comprising 1,3,4-tribenzyl-1,2,4-triazolium chloride and a metal-based catalyst.

[0007] According to the catalytic system provided by the present invention, the silanol is selected from α,ω-dihydroxypolydimethylsiloxane; the siloxane crosslinking agent is selected from methyltrimethoxysilane and / or methyltriethoxysilane.

[0008] According to the catalytic system provided by the present invention, the metal-based catalyst includes an organotitanium catalyst and / or an organotin catalyst.

[0009] According to the catalytic system provided by the present invention, the mass ratio of the 1,3,4-tribenzyl-1,2,4-triazolium chloride to the metal-based catalyst is (1~3):(23~26).

[0010] According to the catalytic system provided by the present invention, the catalytic system further includes: a coupling agent; Preferably, the coupling agent is selected from one or more of γ-(2,3-epoxypropoxy)propyltrimethoxysiloxane, γ-aminopropyltriethoxysilane, and N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, and is preferably γ-aminopropyltriethoxysilane.

[0011] According to the catalytic system provided by the present invention, the catalytic system further includes: a filler; preferably, the filler is selected from nano-calcium carbonate.

[0012] According to the catalytic system provided by the present invention, the catalytic system further includes: a lubricant; the lubricant is selected from dimethyl silicone oil.

[0013] The present invention also provides a two-component dealcohol condensation type organosilicon adhesive, comprising: the catalyst system described above.

[0014] According to the two-component de-alcohol condensation type silicone adhesive provided by the present invention, the surface drying time of the two-component de-alcohol condensation type silicone adhesive is less than or equal to 5 minutes, preferably 2 to 5 minutes.

[0015] According to the two-component de-alcohol condensation type silicone adhesive provided by the present invention, the base adhesive of the two-component de-alcohol condensation type silicone adhesive includes silanol, optional filler and lubricant; Preferably, the two-component dealcohol condensation type silicone adhesive comprises component A and component B; Component A includes silanol, optional filler, lubricant, siloxane crosslinking agent, optional coupling agent, and 1,3,4-tribenzyl-1,2,4-triazolium chloride; Component B includes silanol, optional fillers, lubricants, and metal-based catalysts.

[0016] The present invention also provides a method for preparing the two-component dealcohol condensation type silicone adhesive as described above, wherein the two-component dealcohol condensation type silicone adhesive comprises component A and component B; Component A includes silanol, optional filler, lubricant, siloxane crosslinking agent, optional coupling agent, and 1,3,4-tribenzyl-1,2,4-triazolium chloride; Component B includes silanol, optional fillers, lubricants, and metal-based catalysts.

[0017] The present invention provides a catalytic system, a two-component fast-curing alcohol-de-ethanol condensation type silicone adhesive and its preparation method. From the perspective of catalyst system optimization, it was found that the use of 1,3,4-tribenzyl-1,2,4-triazolium chloride and metal-based catalyst in combination can significantly shorten the surface drying time (achieving rapid curing) while enabling the siloxane segments to form a dense and uniform cross-linked network, thereby obtaining excellent mechanical properties.

[0018] Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. Detailed Implementation

[0019] The embodiments of the present invention will be described in further detail below with reference to examples. These examples are for illustrative purposes only and should not be construed as limiting the scope of the invention.

[0020] In the description of this specification, the references to terms such as "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., refer to specific features, structures, materials, or characteristics described in connection with that embodiment or example, which are included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples. Moreover, without contradiction, those skilled in the art can combine and integrate the different embodiments or examples described in this specification, as well as the features of different embodiments or examples.

[0021] In a specific embodiment of the present invention, a catalytic system is first provided, comprising a condensation reaction between silanol and a siloxane crosslinking agent, and a catalyst composition for improving the rate of the condensation reaction, wherein the catalyst composition comprises 1,3,4-tribenzyl-1,2,4-triazolium chloride and a metal-based catalyst.

[0022] 1,3,4-Tribenzyl-1,2,4-triazolium chloride is a highly potent σ-electron-donating ligand that significantly enhances the electron density and catalytic activity of metal centers. It possesses strong electron-donating capabilities and superior metal center activation ability. Furthermore, the triazolium salt, as a highly efficient precursor to nitrogen-containing heterocyclic carbenes (NHCs), generates the corresponding triazol-5-ylcarbene during the curing reaction. This carbene, as one of the most potent σ-electron-donating ligands, can inject a high electron density into the active metal centers of metal-based catalysts such as tin (Sn) or titanium (Ti), greatly enhancing the electrophilicity of the metal catalytic center. This inherently provides a more powerful catalytic promotion effect, making the binding and activation of silanol (Si-OH) oxygen atoms by the metal center more efficient, directly and significantly improving the initial velocity of the condensation reaction and the overall curing kinetics. Moreover, experiments have shown that the catalytic system of 1,3,4-tribenzyl-1,2,4-triazolium chloride and the metal-based catalyst does not degrade the mechanical properties of the condensation reaction products.

[0023] In some specific embodiments of the present invention, in the catalytic system, the mass ratio of the catalyst composition to the silanol is (21~28):(400~500). For example, it can be any value or a numerical range composed of any values ​​among 21:400, 22:450, and 23:500.

[0024] In some specific embodiments of the present invention, in the catalytic system, the mass ratio of the siloxane crosslinking agent to the silanol is (50~70):(400~500). For example, it can be any value or a numerical range composed of any values ​​among 50:400, 60:450, and 70:500.

[0025] In some specific embodiments of the present invention, the silanol is selected from α,ω-dihydroxypolydimethylsiloxane; the siloxane crosslinking agent is selected from methyltrimethoxysilane and / or methyltriethoxysilane.

[0026] In some specific embodiments of the present invention, the silanol includes a silanol of first viscosity and a silanol of second viscosity; the viscosity of the silanol of first viscosity is higher than the viscosity of the silanol of second viscosity.

[0027] In some specific embodiments of the present invention, the viscosity of the first viscosity silanol is 70,000 to 90,000 mPa·s. For example, it can be any value or a range of values ​​among 70,000 mPa·s, 75,000 mPa·s, 80,000 mPa·s, 85,000 mPa·s, and 90,000 mPa·s.

[0028] In some specific embodiments of the present invention, the viscosity of the second viscosity silanol is 10,000 to 30,000 mPa·s. For example, it can be any value or a range of values ​​among 10,000 mPa·s, 15,000 mPa·s, 20,000 mPa·s, 25,000 mPa·s, and 30,000 mPa·s.

[0029] In some specific embodiments of the present invention, in the catalytic system, the mass ratio of the silanol with the second viscosity to the silanol with the first viscosity is 1:(1~1.5). For example, it can be any value or a range of values ​​from 1:1.0, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5.

[0030] In some specific embodiments of the present invention, the metal-based catalyst includes organotitanium catalysts and / or organotin catalysts.

[0031] In some specific embodiments of the present invention, the mass ratio of the 1,3,4-tribenzyl-1,2,4-triazolium chloride to the metal-based catalyst is (1~3):(23~26). For example, it can be any value or a numerical range composed of any values ​​from 1:23, 1:26, 2:23, 2:26, ​​3:23, 3:26.

[0032] In some specific embodiments of the present invention, the mass ratio of 1,3,4-tribenzyl-1,2,4-triazolium chloride to organotitanium catalyst is (1~3):(14~18); In some specific embodiments of the present invention, the mass ratio of 1,3,4-tribenzyl-1,2,4-triazolium chloride to organotin catalyst is (1~3):(5~8).

[0033] In some specific embodiments of the present invention, the organotitanium catalyst is selected from one or more combinations of isopropyl titanate, n-butyl titanate, and bis(ethyl acetoacetate) titanate chelate.

[0034] In some specific embodiments of the present invention, the organotin catalyst is selected from dibutyltin dilaurate.

[0035] Using the above-mentioned specific catalyst composition for the catalysis of two-component alcohol-dehydration condensation type silicone adhesives is more conducive to shortening the surface drying time, increasing the curing rate, and having minimal impact on the overall performance.

[0036] While maintaining rapid curing, this invention also optimizes the types and amounts of reinforcing materials and coupling agents, enabling the adhesive to achieve a high level of mechanical properties.

[0037] In some specific embodiments of the present invention, the catalytic system further includes: a coupling agent; In some specific embodiments of the present invention, the coupling agent is selected from one or more combinations of γ-(2,3-epoxypropoxy)propyltrimethoxysiloxane, γ-aminopropyltriethoxysilane, and N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, preferably γ-aminopropyltriethoxysilane; among the effects of different coupling agents on the mechanical properties of the adhesive, γ-aminopropyltriethoxysilane has the best effect.

[0038] Preferably, in the catalytic system, the mass ratio of the coupling agent to the silanol is (5~10):(400~500).

[0039] In some specific embodiments of the present invention, the catalytic system further includes a filler; preferably, the filler is selected from nano-calcium carbonate.

[0040] In some specific embodiments of the present invention, the mass ratio of the nano-calcium carbonate to the silanol is (400~500):(400~500).

[0041] In some specific embodiments of the present invention, the nano-calcium carbonate has a particle size of 50-100 nm and a specific surface area of ​​25-35 m². 2 ·g -1 .

[0042] In some specific embodiments of the present invention, the viscosity of the dimethyl silicone oil is 400~800 mPa·s.

[0043] Within the aforementioned range, increasing the amount of nano-calcium carbonate and α,ω-dihydroxypolydimethylsiloxane with the first viscosity is beneficial for improving mechanical properties.

[0044] In some specific embodiments of the present invention, the catalytic system further includes a lubricant; the lubricant is selected from dimethyl silicone oil.

[0045] In some specific embodiments of the present invention, the mass ratio of the lubricant to the silanol is (90~170):(400~500).

[0046] In some specific embodiments of the present invention, the two-component alcohol-de-alcohol condensation type silicone adhesive includes component A and component B; Component A includes silanol, optional filler, lubricant, 1,3,4-tribenzyl-1,2,4-triazolium chloride, siloxane crosslinking agent, and optional coupling agent; Component B includes: silanol, optional filler, lubricant, and metal-based catalyst.

[0047] In some specific embodiments of the present invention, component A, by mass parts, comprises: 200-250 parts of silanol, 200-250 parts of filler, 30-50 parts of lubricant, 60-70 parts of siloxane crosslinking agent, 0-10 parts of coupling agent, and 1,3,4-tribenzyl-1,2,4-triazolium chloride.

[0048] In some specific embodiments of the present invention, the B component, by mass parts, comprises: 200-250 parts of silanol, 200-250 parts of filler, 60-120 parts of lubricant, and a metal-based catalyst.

[0049] Generally, component A and component B are mixed in a volume ratio of 1:1.

[0050] In a specific embodiment of the present invention, a two-component dealcoholization condensation type organosilicone adhesive is also provided, comprising: the catalyst system described above.

[0051] In some specific embodiments of the present invention, the surface drying time of the two-component de-alcoholized condensation type silicone adhesive is less than or equal to 5 minutes, preferably 2 to 5 minutes.

[0052] In some specific embodiments of the present invention, the base adhesive of the two-component de-alcoholized condensation type silicone adhesive includes silanol, optional filler and lubricant; Preferably, the two-component dealcohol condensation type silicone adhesive comprises component A and component B; Component A includes silanol, optional filler, lubricant, siloxane crosslinking agent, optional coupling agent, and 1,3,4-tribenzyl-1,2,4-triazolium chloride; Component B includes silanol, optional fillers, lubricants, and metal-based catalysts.

[0053] In a specific embodiment of the present invention, a method for preparing the two-component dealcohol condensation type silicone adhesive as described above is also provided, wherein the two-component dealcohol condensation type silicone adhesive includes component A and component B; Component A includes silanol, optional filler, lubricant, siloxane crosslinking agent, optional coupling agent, and 1,3,4-tribenzyl-1,2,4-triazolium chloride; Component B includes silanol, optional fillers, lubricants, and metal-based catalysts.

[0054] In some specific embodiments of the present invention, the preparation method includes: First, the silanol and lubricant are thoroughly mixed in a vacuum disperser until the rubber compound is milky white. Then, the filler is added. The temperature is then raised to 100~120℃ and mixed under a vacuum of -0.06~-0.09MPa to obtain base rubber compound I. Then, base rubber compound I, siloxane crosslinking agent, coupling agent and 1,3,4-tribenzyl-1,2,4-triazolium chloride are mixed and added to a planetary vacuum degassing mixer and mixed under vacuum to obtain component A.

[0055] First, the silanol and lubricant are thoroughly mixed in a vacuum disperser until the rubber compound is milky white. Then, the filler is added. The temperature is then raised to 100~120℃ and mixed under a vacuum of -0.06~-0.09MPa to obtain base rubber compound II. Then, base rubber compound II, lubricant, and metal-based catalyst are mixed and added to a planetary vacuum degassing mixer and mixed under vacuum to obtain component B.

[0056] The following will describe in detail the above-mentioned catalytic system, the two-component rapid curing de-alcohol condensation type organosilicon adhesive and its preparation method, with reference to some specific embodiments of the present invention.

[0057] Where specific techniques or conditions are not specified in the examples, they shall be performed in accordance with the techniques or conditions described in the literature in this field, or in accordance with the product instructions. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased through legitimate channels. The structures of some raw materials are as follows: Nano-calcium carbonate: Particle size: 60 nm, specific surface area: 30.0 ± 1.0 m² 2 ·g -1 .

[0058] Example 1 This embodiment provides a two-component dealcoholization condensation type silicone adhesive, which differs from Example 1 only in the composition and amount of component A and component B, as follows: The composition of component A, by mass parts, is as follows: 100 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 20000 mPa·s 140 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 80,000 mPa·s 32 parts of dimethyl silicone oil with a viscosity of 500 mPa·s 240 parts of nano calcium carbonate Crosslinking agent: 60 parts methyltriethoxysilane Coupling agent: 7 parts γ-aminopropyltriethoxysilane Curing accelerator: 2 parts 1,3,4-tribenzyl-1,2,4-triazolium chloride The composition of component B, by mass parts, is as follows: 100 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 20000 mPa·s 140 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 80,000 mPa·s 90 parts of dimethyl silicone oil with a viscosity of 500 mPa·s 240 parts of nano calcium carbonate 6 parts dibutyltin dilaurate Organotitanium catalyst: 17 parts of bis(ethyl acetoacetate) titanate chelate.

[0059] This embodiment also provides a method for preparing a two-component dealcohol condensation type silicone adhesive, the steps of which are as follows: (1) Preparation of component A: (1.1) First, α,ω-dihydroxypolydimethylsiloxane with a viscosity of 20000 mPa·s, α,ω-dihydroxypolydimethylsiloxane with a viscosity of 80000 mPa·s, and dimethyl silicone oil with a viscosity of 500 mPa·s were stirred in a vacuum disperser at 60℃ and 600 r / min for 1 h. After thorough mixing, the adhesive material was milky white. Then, nano-calcium carbonate was added in three portions. The temperature was then raised to 110℃, and the mixture was stirred for 60 min under a vacuum of -0.08 MPa and a rotation speed of 120 r / min to obtain the base adhesive material.

[0060] (1.2) The base adhesive, curing accelerator, crosslinking agent and coupling agent obtained in step (1.1) are mixed and added to a planetary vacuum degassing mixer. Under the condition of vacuum degree of -0.08MPa, the mixture is stirred at 1500r / min for 2min, and then extruded and filled to obtain the final product.

[0061] (2) Preparation of component B: (2.1) The base adhesive is prepared in the same way as in step (1.1).

[0062] (2.2) The base adhesive, dimethyl silicone oil, dibutyltin dilaurate and organotitanium catalyst obtained in step (2.1) are mixed and added to a planetary vacuum degassing mixer. Under a vacuum of -0.08MPa, the mixture is centrifuged at 1500r / min for 2min, then extruded and filled to obtain the final product.

[0063] (3) Mix component A and component B evenly at a volume ratio of 1:1.

[0064] Example 2 This embodiment provides a two-component dealcoholization condensation type silicone adhesive, which differs from Example 1 only in the composition and amount of component A and component B, as follows: The composition of component A, by mass parts, is as follows: 100 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 20000 mPa·s 140 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 80,000 mPa·s 32 parts of dimethyl silicone oil with a viscosity of 500 mPa·s 240 parts of nano calcium carbonate Crosslinking agent: 60 parts methyltriethoxysilane Coupling agent: 2 parts γ-(2,3-epoxypropoxy)propyltrimethoxysiloxane and 5 parts γ-aminopropyltriethoxysilane Curing accelerator: 2 parts of 1,3,4-tribenzyl-1,2,4-triazolium chloride.

[0065] The composition of component B, by mass parts, is as follows: 100 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 20000 mPa·s 140 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 80,000 mPa·s 90 parts of dimethyl silicone oil with a viscosity of 500 mPa·s 240 parts of nano calcium carbonate 7 parts dibutyltin dilaurate Organotitanium catalyst: 17 parts of bis(ethyl acetoacetate) titanate chelate.

[0066] Example 3 This embodiment provides a two-component dealcoholization condensation type silicone adhesive, which differs from Example 1 only in the composition and amount of component A and component B, as follows: The composition of component A, by mass parts, is as follows: 100 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 20000 mPa·s 140 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 80,000 mPa·s 32 parts of dimethyl silicone oil with a viscosity of 500 mPa·s 240 parts of nano calcium carbonate Crosslinking agent: 60 parts methyltriethoxysilane Coupling agent: 2 parts N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane and 5 parts γ-aminopropyltriethoxysilane Curing accelerator: 2 parts of 1,3,4-tribenzyl-1,2,4-triazolium chloride.

[0067] The composition of component B, by mass parts, is as follows: 100 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 20000 mPa·s 140 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 80,000 mPa·s 90 parts of dimethyl silicone oil with a viscosity of 500 mPa·s 240 parts of nano calcium carbonate 7 parts dibutyltin dilaurate Organotitanium catalyst: 17 parts of bis(ethyl acetoacetate) titanate chelate.

[0068] Example 4 This embodiment provides a two-component dealcoholization condensation type silicone adhesive, which differs from Example 1 only in the composition and amount of component A and component B, as follows: The composition of component A, by mass parts, is as follows: 100 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 20000 mPa·s 140 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 80,000 mPa·s 32 parts of dimethyl silicone oil with a viscosity of 500 mPa·s 240 parts of nano calcium carbonate Crosslinking agent: 60 parts methyltriethoxysilane Coupling agent: 2 parts γ-(2,3-epoxypropoxy)propyltrimethoxysiloxane and 5 parts γ-aminopropyltriethoxysilane Curing accelerator: 2 parts of 1,3,4-tribenzyl-1,2,4-triazolium chloride.

[0069] The composition of component B, by mass parts, is as follows: 100 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 20000 mPa·s 140 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 80,000 mPa·s 90 parts of dimethyl silicone oil with a viscosity of 500 mPa·s 240 parts of nano calcium carbonate 7 parts dibutyltin dilaurate Organic titanium catalyst: 17 parts tetrabutyl titanate.

[0070] Example 5 This embodiment provides a two-component dealcoholization condensation type silicone adhesive, which differs from Example 1 only in the composition and amount of component A and component B, as follows: The composition of component A, by mass parts, is as follows: 100 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 20000 mPa·s 140 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 80,000 mPa·s 32 parts of dimethyl silicone oil with a viscosity of 500 mPa·s 240 parts of nano calcium carbonate Crosslinking agent: 60 parts methyltriethoxysilane Coupling agent: 2 parts γ-(2,3-epoxypropoxy)propyltrimethoxysiloxane and 5 parts γ-aminopropyltriethoxysilane Curing accelerator: 2 parts of 1,3,4-tribenzyl-1,2,4-triazolium chloride.

[0071] The composition of component B, by mass parts, is as follows: 100 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 20000 mPa·s 140 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 80,000 mPa·s 90 parts of dimethyl silicone oil with a viscosity of 500 mPa·s 240 parts of nano calcium carbonate 7 parts dibutyltin dilaurate Organotitanium catalyst: 17 parts isopropyl titanate.

[0072] Comparative Example 1 The only difference from Example 1 is the composition and amount of component A and component B, which are as follows: The composition of component A, by mass parts, is as follows: 100 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 20000 mPa·s; 100 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 80,000 mPa·s; 30 parts of dimethyl silicone oil with a viscosity of 500 mPa·s; 200 parts of nano-calcium carbonate; Crosslinking agent: 50 parts methyltrimethoxysilane Coupling agent: 6 parts γ-aminopropyltriethoxysilane; The composition of component B, by mass parts, is as follows: 100 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 20000 mPa·s; 100 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 80,000 mPa·s; 90 parts of dimethyl silicone oil with a viscosity of 500 mPa·s; 200 parts of nano-calcium carbonate; 5 parts dibutyltin dilaurate; Organotitanium catalyst: 14 parts of bis(ethyl acetoacetate) titanate chelate.

[0073] Comparative Example 2 The only difference from Example 1 is the composition and amount of component A and component B, which are as follows: The composition of component A, by mass parts, is as follows: 100 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 20000 mPa·s 130 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 80,000 mPa·s 30 parts of dimethyl silicone oil with a viscosity of 500 mPa·s 215 parts of nano calcium carbonate Crosslinking agent: 55 parts methyltrimethoxysilane Coupling agent: 7 parts γ-aminopropyltriethoxysilane The composition of component B, by mass parts, is as follows: 100 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 20000 mPa·s 130 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 80,000 mPa·s 90 parts of dimethyl silicone oil with a viscosity of 500 mPa·s 6 parts dibutyltin dilaurate Organotitanium catalyst: 14 parts of bis(ethyl acetoacetate) titanate chelate.

[0074] Comparative Example 3 The only difference from Example 1 is the composition and amount of component A and component B, which are as follows: The composition of component A, by mass parts, is as follows: 100 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 20000 mPa·s 140 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 80,000 mPa·s 32 parts of dimethyl silicone oil with a viscosity of 500 mPa·s 240 parts of nano calcium carbonate Crosslinking agent: 60 parts methyltrimethoxysilane Coupling agent: 7 parts γ-aminopropyltriethoxysilane The composition of component B, by mass parts, is as follows: 100 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 20000 mPa·s 140 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 80,000 mPa·s 90 parts of dimethyl silicone oil with a viscosity of 500 mPa·s 240 parts of nano calcium carbonate 6 parts dibutyltin dilaurate Organotitanium catalyst: 17 parts of bis(ethyl acetoacetate) titanate chelate.

[0075] Example 6 The only difference from Example 1 is that the composition and amount of component A are as follows: The composition of component A, by mass parts, is as follows: 100 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 20000 mPa·s 150 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 80,000 mPa·s 42 parts of dimethyl silicone oil with a viscosity of 500 mPa·s 250 parts nano calcium carbonate Crosslinking agent: 65 parts methyltrimethoxysilane Coupling agent: 8 parts γ-aminopropyltriethoxysilane.

[0076] Curing accelerator: 2 parts of 1,3,4-tribenzyl-1,2,4-triazolium chloride.

[0077] The composition of component B, by mass parts, is as follows: 100 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 20000 mPa·s 150 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 80,000 mPa·s 90 parts of dimethyl silicone oil with a viscosity of 500 mPa·s 250 parts nano calcium carbonate 7 parts dibutyltin dilaurate Organotitanium catalyst: 17 parts of bis(ethyl acetoacetate) titanate chelate.

[0078] Example 7 The only difference from Example 1 is the composition and amount of component A and component B, which are as follows: The composition of component A, by mass parts, is as follows: 100 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 20000 mPa·s 140 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 80,000 mPa·s 32 parts of dimethyl silicone oil with a viscosity of 500 mPa·s 240 parts of nano calcium carbonate Crosslinking agent: 70 parts methyltriethoxysilane Coupling agent: 7 parts γ-aminopropyltriethoxysilane Curing accelerator: 2 parts of 1,3,4-tribenzyl-1,2,4-triazolium chloride.

[0079] The composition of component B, by mass parts, is as follows: 100 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 20000 mPa·s 140 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 80,000 mPa·s 90 parts of dimethyl silicone oil with a viscosity of 500 mPa·s 240 parts of nano calcium carbonate 7 parts dibutyltin dilaurate Organotitanium catalyst: 17 parts of bis(ethyl acetoacetate) titanate chelate.

[0080] Example 8 The only difference from Example 1 is the composition and amount of component A and component B, which are as follows: The composition of component A, by mass parts, is as follows: 100 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 20000 mPa·s 140 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 80,000 mPa·s 32 parts of dimethyl silicone oil at 500 mPa·s 240 parts of nano calcium carbonate Crosslinking agent: 60 parts methyltriethoxysilane Coupling agent: 7 parts γ-aminopropyltriethoxysilane Curing accelerator: 1 part 1,3,4-tribenzyl-1,2,4-triazolium chloride.

[0081] The composition of component B, by mass parts, is as follows: 100 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 20000 mPa·s 140 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 80,000 mPa·s 90 parts of dimethyl silicone oil at 500 mPa·s 240 parts of nano calcium carbonate 7 parts dibutyltin dilaurate Organotitanium catalyst: 17 parts of bis(ethyl acetoacetate) titanate chelate.

[0082] Example 9 The only difference from Example 1 is the composition and amount of component A and component B, which are as follows: The composition of component A, by mass parts, is as follows: 100 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 20000 mPa·s 140 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 80,000 mPa·s 32 parts of dimethyl silicone oil with a viscosity of 500 mPa·s 240 parts of nano calcium carbonate Crosslinking agent: 60 parts methyltriethoxysilane Coupling agent: 7 parts γ-aminopropyltriethoxysilane Curing accelerator: 3 parts of 1,3,4-tribenzyl-1,2,4-triazolium chloride.

[0083] The composition of component B, by mass parts, is as follows: 100 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 20000 mPa·s 140 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 80,000 mPa·s 90 parts of dimethyl silicone oil with a viscosity of 500 mPa·s 240 parts of nano calcium carbonate 7 parts dibutyltin dilaurate Organotitanium catalyst: 17 parts of bis(ethyl acetoacetate) titanate chelate.

[0084] Example 10 The only difference from Example 1 is the composition and amount of component A and component B, which are as follows: The composition of component A, by mass parts, is as follows: 100 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 20000 mPa·s 140 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 80,000 mPa·s 32 parts of dimethyl silicone oil with a viscosity of 500 mPa·s 240 parts of nano calcium carbonate Crosslinking agent: 60 parts methyltriethoxysilane Coupling agent: 7 parts γ-aminopropyltriethoxysilane Curing accelerator: 2 parts of 1,3,4-tribenzyl-1,2,4-triazolium chloride.

[0085] The composition of component B, by mass parts, is as follows: 100 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 20000 mPa·s 140 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 80,000 mPa·s 90 parts of dimethyl silicone oil with a viscosity of 500 mPa·s 240 parts of nano calcium carbonate 8 parts dibutyltin dilaurate Organotitanium catalyst: 18 parts of bis(ethyl acetoacetate) titanate chelate.

[0086] Example 11 The only difference from Example 1 is the composition and amount of component A and component B, which are as follows: The composition of component A, by mass parts, is as follows: 100 parts have a viscosity of 20000 mPa·s 140 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 80,000 mPa·s 32 parts of dimethyl silicone oil with a viscosity of 500 mPa·s 240 parts of nano calcium carbonate Crosslinking agent: 60 parts methyltriethoxysilane Coupling agent: 7 parts γ-(2,3-epoxypropoxy)propyltrimethoxysiloxane Curing accelerator: 2 parts of 1,3,4-tribenzyl-1,2,4-triazolium chloride.

[0087] The composition of component B, by mass parts, is as follows: 100 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 20000 mPa·s 140 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 80,000 mPa·s 90 parts of dimethyl silicone oil with a viscosity of 500 mPa·s 240 parts of nano calcium carbonate 7 parts dibutyltin dilaurate Organotitanium catalyst: 17 parts of bis(ethyl acetoacetate) titanate chelate.

[0088] Example 12 The only difference from Example 1 is the composition and amount of component A and component B, which are as follows: The composition of component A, by mass parts, is as follows: 100 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 20000 mPa·s 140 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 80,000 mPa·s 32 parts of dimethyl silicone oil with a viscosity of 500 mPa·s 240 parts of nano calcium carbonate Crosslinking agent: 60 parts methyltriethoxysilane Coupling agent: 7 parts N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane Curing accelerator: 2 parts of 1,3,4-tribenzyl-1,2,4-triazolium chloride.

[0089] The composition of component B, by mass parts, is as follows: 100 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 20000 mPa·s 140 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 80,000 mPa·s 90 parts of dimethyl silicone oil with a viscosity of 500 mPa·s 240 parts of nano calcium carbonate 7 parts dibutyltin dilaurate Organotitanium catalyst: 17 parts of bis(ethyl acetoacetate) titanate chelate.

[0090] Test Example 1 The adhesives prepared in Examples 1-10 above were tested for surface drying time, shear strength, and tensile strength according to GB / T 13477-2002, GB / T 528-2009, and GB / T 7124-2008. The results are shown in Table 1. Table 1

[0091] As shown in the table above, the adhesives of this invention have relatively short surface drying times, all within 5 minutes, and exhibit high mechanical properties. The mechanical properties of the adhesive gradually improve with increasing amounts of high-viscosity α,ω-dihydroxypolydimethylsiloxane and reinforcing nano-calcium carbonate. The experiments also revealed the influence of different coupling agents on the mechanical properties of the adhesives, with γ-aminopropyltriethoxysilane showing the best effect. In Comparative Examples 1-3, the surface drying time was relatively long due to the absence of 1,3,4-tribenzyl-1,2,4-triazolium chloride. In other examples where 1,3,4-tribenzyl-1,2,4-triazolium chloride curing accelerator was added, the surface drying time of the adhesive was significantly reduced, the curing speed was significantly accelerated, and the shear strength and tensile strength of the adhesive remained at relatively high values. However, excessive addition may affect the cross-linking network of the adhesive, leading to a decrease in mechanical properties. Therefore, it is necessary to balance the proportions of each component in order to maintain rapid curing while keeping the mechanical properties of the adhesive at a high level.

[0092] Finally, it should be noted that the above embodiments are only for illustrating the present invention and not for limiting the present invention. Although the present invention has been described in detail with reference to the embodiments, those skilled in the art should understand that various combinations, modifications, or equivalent substitutions of the technical solutions of the present invention do not depart from the spirit and scope of the technical solutions of the present invention and should be covered within the scope of the claims of the present invention.

Claims

1. A catalytic system, characterized in that, The invention includes a condensation reaction between silanol and a siloxane crosslinking agent, and a catalyst composition for improving the rate of the condensation reaction, the catalyst composition comprising 1,3,4-tribenzyl-1,2,4-triazolium chloride and a metal-based catalyst.

2. The catalytic system according to claim 1, characterized in that, The silanol is selected from α,ω-dihydroxypolydimethylsiloxane; the siloxane crosslinking agent is selected from methyltrimethoxysilane and / or methyltriethoxysilane.

3. The catalytic system according to claim 1 or 2, characterized in that, The metal-based catalysts include organotitanium catalysts and / or organotin catalysts.

4. The catalytic system according to any one of claims 1 to 3, characterized in that, The mass ratio of the 1,3,4-tribenzyl-1,2,4-triazolium chloride to the metal-based catalyst is (1~3):(23~26).

5. The catalytic system according to any one of claims 1 to 4, characterized in that, The catalytic system further includes: a coupling agent; Preferably, the coupling agent is selected from one or more of γ-(2,3-epoxypropoxy)propyltrimethoxysiloxane, γ-aminopropyltriethoxysilane, and N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, and is preferably γ-aminopropyltriethoxysilane.

6. The catalytic system according to any one of claims 1 to 5, characterized in that, The catalytic system further includes a filler; preferably, the filler is selected from nano-calcium carbonate.

7. The catalytic system according to any one of claims 1 to 6, characterized in that, The catalytic system further includes a lubricant; the lubricant is selected from dimethyl silicone oil.

8. A two-component dealcoholization condensation type silicone adhesive, characterized in that, include: The catalyst system according to any one of claims 1 to 7.

9. The two-component dealcoholization condensation type silicone adhesive according to claim 8, characterized in that, The surface drying time of the two-component de-alcoholized condensation type silicone adhesive is less than or equal to 5 minutes, preferably 2 to 5 minutes.

10. The method for preparing the two-component dealcoholization condensation type silicone adhesive according to claim 8 or 9, characterized in that, The two-component alcohol-de-alcohol condensation type silicone adhesive includes component A and component B; Component A includes silanol, optional filler, lubricant, siloxane crosslinking agent, optional coupling agent, and 1,3,4-tribenzyl-1,2,4-triazolium chloride; Component B includes silanol, optional fillers, lubricants, and metal-based catalysts.

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