High-compression-resilience organic silicon sealant and preparation method thereof

Abstract

The invention relates to a high-compression-resilience organic silicon sealant and a preparation method thereof, and belongs to the technical field of organic silicon modification. The high-compression-resilience organic silicon sealant is prepared from the following components in parts by weight: 20 to 35 parts of methyl vinyl MQ resin, 30 to 50 parts of vinyl silicone oil 1, 30 to 50 parts of vinyl silicone oil 2, 1 to 3 parts of silane coupling agent, 3 to 9 parts of hydrogen-containing silicone oil, 5 to 20 parts of white carbon black, 0.02 to 0.1 part of Pt catalyst, 0.02 to 0.1 part of inhibitor and 0.03 to 0.5 part of black color paste. According to the invention, the vinyl silicone oil 1 is added, so that the rebound resilience of the sealant is improved; the vinyl silicone oil 2 is added, so that the toughness of the sealant is improved.

Description

Technical Field

[0001] The invention relates to a high-compression-rebound organic silicon sealant and a preparation method thereof, belonging to the technical field of organic silicon modification. Background Art

[0002] CIPG (inline formed seal ring technology) plays an important role in the manufacturing of new energy vehicles. It provides excellent sealing effects and ensures the sealing performance of battery systems, motors and electronic control systems, cooling systems and other key components, providing important support for the safety, reliability and performance of new energy vehicles. With the continuous development of the new energy vehicle market, CIPG technology will continue to play a key role in promoting innovation and progress in the manufacturing of new energy vehicles. The key point to ensure the excellent effect of the sealant is to have good compression and rebound performance. The compression amount is 30%. After being tested in various high temperature environments, the rubber strip has no obvious deformation or corrosion. After releasing the pressure, it can quickly rebound to at least 95% before compression. Ordinary silicone is difficult to meet this requirement. Summary of the invention

[0003] The purpose of the present invention is to solve the shortcomings of the prior art and disclose a high compression rebound organic silicon sealant and a preparation method thereof. The vinyl silicone oil 1 used in the sealant improves the resilience of the sealant; the addition of the vinyl silicone oil 2 improves the toughness of the sealant.

[0004] One of the purposes of the present invention is to provide a high compression and resilience organic silicone sealant, which comprises, by weight, 20 to 35 parts of methyl vinyl MQ resin, 30 to 50 parts of vinyl silicone oil 1, 30 to 50 parts of vinyl silicone oil 2, 1 to 3 parts of silane coupling agent, 3 to 9 parts of hydrogenated silicone oil, 5 to 20 parts of white carbon black, 0.02 to 0.1 parts of Pt catalyst, 0.02 to 0.1 parts of inhibitor, and 0.03 to 0.5 parts of black color paste;

[0005] The structure of the vinyl silicone oil 1 is:

[0006]

[0007] Among them, the value range of m, n, and o is an integer greater than or equal to 1;

[0008] The structure of the vinyl silicone oil 2 is:

[0009]

[0010] The value range of x is an integer greater than or equal to 1.

[0011] The vinyl content of the methyl vinyl MQ resin is 0.35-0.6 mmol / g, and the viscosity at 25° C. is 4000-10000 mPa.S.

[0012] The silane coupling agent is at least one of methacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane and allyltrimethoxysilane.

[0013] The hydrogen content of the hydrogen-containing silicone oil is 0.25-10 mmol / g, and the viscosity is 25-80 mPa.S at 25° C.; the white carbon black is a hydrophobic white carbon black with a specific surface area of ​​140-250 m2 / g.

[0014] The Pt catalyst is a vinylsiloxane complex of chloroplatinic acid, and the platinum content is 2500-6500 ppm; the inhibitor is at least one of 3-methyl-1-butyn-3-ol, trimethyl-1-pentyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, and 1-ethynyl-1-cyclohexanol.

[0015] The black color paste is a universal color paste mixed with silicone oil and nano carbon black purchased from the market.

[0016] The second object of the present invention is to provide a method for preparing the high compression rebound organic silicone sealant, comprising the following steps: according to weight parts, 20 to 35 parts of methyl vinyl MQ resin, 30 to 50 parts of vinyl silicone oil 1, 30 to 50 parts of vinyl silicone oil 2, 1 to 3 parts of silane coupling agent, 3 to 9 parts of hydrogen-containing silicone oil, 5 to 20 parts of white carbon black, 0.02 to 0.1 parts of Pt catalyst, 0.02 to 0.1 parts of inhibitor, and 0.03 to 0.5 parts of black color paste are mixed to obtain.

[0017] The preparation method of the vinyl silicone oil 1 comprises the following steps: adding tetramethyl divinyl disiloxane, hexaphenyl cyclotrisiloxane, octamethyl cyclotetrasiloxane and tetramethyl tetravinyl cyclotetrasiloxane into a reaction container, stirring at room temperature for 15-30 minutes, then adding tetramethyl ammonium hydroxide, slowly heating the temperature to 95-115° C., stirring for 2-8 hours, then raising the temperature to 150-160° C., stirring for 2-8 hours under a vacuum condition with a vacuum degree of less than 0.085 MPa, and obtaining the vinyl silicone oil 1. The molar ratio of the tetramethyl divinyl disiloxane, hexaphenyl cyclotrisiloxane, octamethyl cyclotetrasiloxane and tetramethyl tetravinyl cyclotetrasiloxane is 1-3:1-3:2-6:5-20.

[0018] The reaction formula is:

[0019]

[0020] The value range of m, n, and o is an integer greater than or equal to 1.

[0021] The preparation method of the vinyl silicone oil 2 comprises the following steps: adding methyltrimethoxysilane, dimethyldimethoxysilane and hexavinyldisiloxane in a molar ratio of 1-1.5:10-30:1.5-5 to a reaction vessel equipped with a water separation device, slowly dripping a sulfuric acid aqueous solution of 0.5-5% of the total mass of the above silanes under stirring at room temperature, wherein the mass concentration of sulfuric acid in the sulfuric acid aqueous solution is 1%-7%, then reacting at 55-75°C for 0.5-1.5 hours, setting the oil temperature to 85-90°C to separate the generated small molecule alcohol for 2-3 hours, then adding toluene 1-2 times the weight of the system, reacting and removing water at 95-100°C for 3-5 hours, and finally removing toluene at 95-110°C under vacuum conditions of less than 0.085Mpa to obtain vinyl silicone oil 2. The reaction formula is:

[0022]

[0023] The value range of x is an integer greater than or equal to 1.

[0024] Compared with the prior art, the beneficial effects of the present invention are as follows: the vinyl silicone oil 1 is used in the sealant prepared by the present invention, thereby improving the resilience of the sealant; the addition of the vinyl silicone oil 2 improves the toughness of the sealant while maintaining a certain elasticity. DETAILED DESCRIPTION

[0025] The present invention is described below in conjunction with examples, which are only used to explain the present invention and are not used to limit the scope of the present invention.

[0026] In a three-necked flask, 18.6 g of tetramethyldivinyldisiloxane, 59.5 g of hexaphenylcyclotrisiloxane, 59.3 g of octamethylcyclotetrasiloxane, and 344 g of tetramethyltetravinylcyclotetrasiloxane were added, and the mixture was stirred at room temperature for 20 min. 0.1 g of tetramethylammonium hydroxide was added, and the temperature was slowly raised to 100° C. After stirring for 4 h, the temperature was raised to 160° C. and stirred for 4 h under a vacuum condition with a vacuum degree of less than 0.085 MPa to obtain vinyl silicone oil 1.

[0027] 13.6 g of methyltrimethoxysilane, 240 g of dimethyldimethoxysilane and 35.1 g of hexavinyldisiloxane were added to a four-necked flask with a water separator. Under stirring at room temperature, 2 g of a 1% sulfuric acid aqueous solution was slowly dripped in, followed by reaction at 60° C. for 1 hour. The oil temperature was set to 85° C. to separate the generated small molecule alcohol for 2 hours. Subsequently, toluene in an amount 1 times the weight of the system (the total weight of all the aforementioned substances) was added, and the reaction was carried out at 100° C. to remove water for 4 hours. Finally, the high temperature of 110° C. was maintained under vacuum conditions with a vacuum degree of less than 0.085 MPa to remove the toluene solvent to obtain vinyl silicone oil 2.

[0028] Example 1

[0029] Methyl vinyl MQ resin (vinyl content 0.6mmol / g, viscosity at 25℃ 6000mPa.S), vinyl silicone oil 1, vinyl silicone oil 2, methacryloxypropyl trimethoxysilane, hydrogen-containing silicone oil (hydrogen-containing silicone oil hydrogen content 5.5mmol / g, viscosity at 25℃ 30mPa.S), white carbon black (specific surface area 180m 2 / g of hydrophobic silica), Pt catalyst (vinylsiloxane complex of chloroplatinic acid, platinum content of 2500ppm), 3-methyl-1-butyn-3-ol, and black paste are mixed in a weight ratio of 25:30:30:2:3.5:12:0.1:0.06:0.5.

[0030] Example 2

[0031] Methyl vinyl MQ resin (vinyl content 0.6mmol / g, viscosity at 25℃ 6000mPa.S), vinyl silicone oil 1, vinyl silicone oil 2, methacryloxypropyl trimethoxysilane, hydrogen-containing silicone oil (hydrogen-containing silicone oil hydrogen content 5.5mmol / g, viscosity at 25℃ 30mPa.S), white carbon black (specific surface area 180m 2 / g of hydrophobic silica), Pt catalyst (vinylsiloxane complex of chloroplatinic acid, platinum content of 2500ppm), 3-methyl-1-butyn-3-ol, and black paste are mixed in a weight ratio of 25:40:20:2:3.5:12:0.1:0.06:0.5.

[0032] Example 3

[0033] Methyl vinyl MQ resin (vinyl content 0.6mmol / g, viscosity at 25℃ 6000mPa.S), vinyl silicone oil 1, vinyl silicone oil 2, methacryloxypropyl trimethoxysilane, hydrogen-containing silicone oil (hydrogen-containing silicone oil hydrogen content 5.5mmol / g, viscosity at 25℃ 30mPa.S), white carbon black (specific surface area 180m 2 / g of hydrophobic silica), Pt catalyst (vinylsiloxane complex of chloroplatinic acid, platinum content of 2500ppm), 3-methyl-1-butyn-3-ol, and black paste are mixed in a weight ratio of 25:20:40:2:3.5:12:0.1:0.06:0.5.

[0034] Comparative Example 1

[0035] Methyl vinyl MQ resin (vinyl content 0.6mmol / g, viscosity at 25℃ 6000mPa.S), vinyl silicone oil 1, methacryloxypropyl trimethoxysilane, hydrogen-containing silicone oil (hydrogen-containing silicone oil hydrogen content 5.5mmol / g, viscosity at 25℃ 30mPa.S), white carbon black (specific surface area 180m 2 / g of hydrophobic silica), Pt catalyst (vinylsiloxane complex of chloroplatinic acid, platinum content of 2500ppm), 3-methyl-1-butyn-3-ol, and black color paste are mixed in a weight ratio of 25:60:2:3.5:12:0.1:0.06:0.5.

[0036] Comparative Example 2

[0037] Methylvinyl MQ resin (vinyl content 0.6mmol / g, viscosity at 25℃ 6000mPa.S), vinyl silicone oil 2, methacryloxypropyl trimethoxysilane, hydrogen-containing silicone oil (hydrogen-containing silicone oil hydrogen content 5.5mmol / g, viscosity at 25℃ 30mPa.S), white carbon black (specific surface area 180m 2 / g of hydrophobic silica), Pt catalyst (vinylsiloxane complex of chloroplatinic acid, platinum content of 2500ppm), 3-methyl-1-butyn-3-ol, and black color paste are mixed in a weight ratio of 25:60:2:3.5:12:0.1:0.06:0.5.

[0038] Comparative Example 3

[0039] Methyl vinyl MQ resin (vinyl content 0.6mmol / g, viscosity at 25℃ 6000mPa.S), double-terminal vinyl silicone oil (vinyl content 0.06mmol / g, viscosity at 25℃ 5000mPa.S), methacryloxypropyl trimethoxysilane, hydrogen-containing silicone oil (hydrogen-containing silicone oil hydrogen content 5.5mmol / g, viscosity at 25℃ 30mPa.S), white carbon black (specific surface area 180m 2 / g of hydrophobic silica), Pt catalyst (vinylsiloxane complex of chloroplatinic acid, platinum content of 2500ppm), 3-methyl-1-butyn-3-ol, and black paste are mixed in a weight ratio of 25:30:2:3.5:12:0.1:0.06:0.5.

[0040] The properties of the samples are shown in Table 1, and the test methods are described in Table 1.

[0041] Table 1. Performance test results

[0042]

[0043]

[0044] Compared with Examples 2 and 3, the effect of adding vinyl silicone oil 1 on compression rebound gradually decreases when it reaches a certain value. As the amount of vinyl silicone oil 2 decreases, the effect on tear strength is greater. Compared with Comparative Examples 1, 2, and 3, it can be seen from Example 1 that vinyl silicone oil 1 can reduce the compression loss rate of the sealant. This is due to the presence of appropriate side vinyl groups in the silicone oil. At the same time, the appropriate amount of phenyl groups contained in vinyl silicone oil 1 increases the steric hindrance and makes the deformation of the cross-linked structure more difficult. Therefore, its effect of reducing the compression loss rate of the sealant is more obvious. The appropriate amount of T structure in vinyl silicone oil 2 increases the tear resistance of the colloid.

[0045] The above description is only a preferred embodiment of the present invention and is not intended to limit the scope of the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the concept and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A high compression rebound silicone sealant, characterized in that: According to weight parts, it contains 20 to 35 parts of methyl vinyl MQ resin, 30 to 50 parts of vinyl silicone oil 1, 30 to 50 parts of vinyl silicone oil 2, 1 to 3 parts of silane coupling agent, 3 to 9 parts of hydrogenated silicone oil, 5 to 20 parts of white carbon black, 0.02 to 0.1 parts of Pt catalyst, 0.02 to 0.1 parts of inhibitor, and 0.03 to 0.5 parts of black color paste; The structure of the vinyl silicone oil 1 is: Among them, the value range of m, n, and o is an integer greater than or equal to 1; The structure of the vinyl silicone oil 2 is: The value range of x is an integer greater than or equal to 1.

2. The high compression rebound organic silicon sealant according to claim 1, characterized in that: The vinyl content of the methyl vinyl MQ resin is 0.35-0.6 mmol / g, and the viscosity at 25° C. is 4000-10000 mPa.S.

3. The high compression rebound organic silicon sealant according to claim 1, characterized in that: The silane coupling agent is at least one of methacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane and allyltrimethoxysilane.

4. The high compression rebound organic silicon sealant according to claim 1, characterized in that: The hydrogen content of the hydrogen-containing silicone oil is 0.25-10 mmol / g, and the viscosity is 25-80 mPa.S at 25°C; the white carbon black has a specific surface area of ​​140-250 m 2 / g of hydrophobic silica.

5. The high compression rebound organic silicon sealant according to claim 1, characterized in that: The Pt catalyst is a vinylsiloxane complex of chloroplatinic acid, and the platinum content is 2500-6500 ppm; the inhibitor is at least one of 3-methyl-1-butyn-3-ol, trimethyl-1-pentyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, and 1-ethynyl-1-cyclohexanol.

6. A method for preparing the high compression resilience organic silicone sealant according to any one of claims 1 to 5, characterized in that: The method comprises the following steps: according to weight parts, 20 to 35 parts of methyl vinyl MQ resin, 30 to 50 parts of vinyl silicone oil 1, 30 to 50 parts of vinyl silicone oil 2, 1 to 3 parts of silane coupling agent, 3 to 9 parts of hydrogen-containing silicone oil, 5 to 20 parts of white carbon black, 0.02 to 0.1 parts of Pt catalyst, 0.02 to 0.1 parts of inhibitor and 0.03 to 0.5 parts of black color paste are mixed to obtain a mixture.

7. The method for preparing the high compression rebound organic silicon sealant according to claim 6, characterized in that: The preparation method of the vinyl silicone oil 1 comprises the following steps: adding tetramethyldivinyldisiloxane, hexaphenylcyclotrisiloxane, octamethylcyclotetrasiloxane and tetramethyltetravinylcyclotetrasiloxane into a reaction container, stirring at room temperature for 15-30 minutes, then adding tetramethylammonium hydroxide, slowly heating the temperature to 95-115° C., stirring for 2-8 hours, then raising the temperature to 150-160° C., stirring for 2-8 hours under a vacuum condition with a vacuum degree of less than 0.085 Mpa, and obtaining the vinyl silicone oil 1.

8. The method for preparing the high compression rebound organic silicon sealant according to claim 7, characterized in that: The molar ratio of the tetramethyldivinyldisiloxane, the hexaphenylcyclotrisiloxane, the octamethylcyclotetrasiloxane and the tetramethyltetravinylcyclotetrasiloxane is 1-3:1-3:2-6:5-20.

9. The method for preparing the high compression rebound organic silicon sealant according to claim 6, characterized in that: The preparation method of the vinyl silicone oil 2 comprises the following steps: adding methyltrimethoxysilane, dimethyldimethoxysilane and hexavinyldisiloxane in a molar ratio of 1-1.5:10-30:1.5-5 into a reaction container with a water separation device, slowly dripping a sulfuric acid aqueous solution with a total mass of 0.5-5% of the above silanes under stirring at room temperature, wherein the mass concentration of sulfuric acid in the sulfuric acid aqueous solution is 1%-7%, then reacting at 55-75° C. for 0.5-1.5 hours, setting the oil temperature to 85-90° C. to separate the generated small molecule alcohol for 2-3 hours, then adding toluene with a mass of 1-2 times the weight of the system, reacting and removing water at 95-100° C. for 3-5 hours, and finally removing toluene at a vacuum condition of maintaining a vacuum degree of less than 0.085 Mpa at 95-110° C. to obtain the vinyl silicone oil 2.

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