阅读说明：本技术 一种耐油、耐高温、低挥发分有机硅胶 (Oil-resistant, high-temperature-resistant and low-volatile organic silica gel ) 是由 王传萍 徐友志 王建斌 陈田安 于 2020-08-14 设计创作，主要内容包括：本发明涉及一种耐油、耐高温、低挥发分有机硅胶,其中甲基乙烯基MQ树脂、甲基硅油、硅烷偶联剂1、硅烷偶联剂2、硅烷偶联剂3、含氢硅油、白炭黑、Pt催化剂、抑制剂、黑色色膏按20～35:40～50：0.5～3：0.5～3：0.5～3：3～9：1～6：0.02～0.1：0.02～0.1：0.03～0.5的重量比混合。本发明所采用的硅烷偶联剂1含有的多个乙氧基,在起到偶联剂作用的同时,还可起到吸水剂的作用,降低体系内水分的含量,从而提高产品的储存稳定性；硅烷偶联剂2含有的两个向邻近的苯环,可提高胶水在高温下的裂解温度；硅烷偶联剂3含有的醚链分子填充于聚硅氧烷分子链间,从而有效的阻隔油分子对胶体的侵蚀。(The invention relates to an oil-resistant, high-temperature-resistant and low-volatile organic silica gel, wherein the weight ratio of methyl vinyl MQ resin, methyl silicone oil, a silane coupling agent 1, a silane coupling agent 2, a silane coupling agent 3, hydrogen-containing silicone oil, white carbon black, a Pt catalyst, an inhibitor and black paste is (20-35: 40-50): 0.5-3: 0.5-3: 0.5-3: 3-9: 1-6: 0.02-0.1: 0.02-0.1: 0.03 to 0.5 by weight. The silane coupling agent 1 adopted by the invention contains a plurality of ethoxy groups, and can play a role of a water absorbent while playing a role of a coupling agent, so that the content of water in a system is reduced, and the storage stability of a product is improved; the silane coupling agent 2 contains two benzene rings which are adjacent to each other, so that the cracking temperature of the glue at high temperature can be increased; the ether chain molecules contained in the silane coupling agent 3 are filled among the polysiloxane molecular chains, so that the corrosion of oil molecules to colloids is effectively prevented.)

1. The oil-resistant, high-temperature-resistant and low-volatile organic silica gel is characterized in that methyl vinyl MQ resin, methyl silicone oil, a silane coupling agent 1, a silane coupling agent 2, a silane coupling agent 3, hydrogen-containing silicone oil, white carbon black, a Pt catalyst, an inhibitor and black color paste are mixed according to a ratio of 20-35: 40-50: 0.5-3: 0.5-3: 0.5-3: 3-9: 1-6: 0.02-0.1: 0.02-0.1: 0.03-0.5 by weight;

the silane coupling agent 1 has the structure

The silane coupling agent 2 has the structure

A chain link is

The silane coupling agent 3 has the structure

2. The silicone rubber according to claim 1, wherein silane coupling agent 1 is prepared by the following method: dissolving pentaerythritol triacrylate and 8-18 ppm of tris (pentafluoro) phenylborane in a reaction system into toluene in a three-neck flask, and stirring for 15-35 min at room temperature to prepare a solution with the mass fraction of 25% -45%; slowly dripping triethoxysilane with the same molar mass as pentaerythritol triacrylate into the system, after dripping is finished, heating to 55-85 ℃, and reacting for 3-5 hours, wherein the negative pressure is less than 0.55 Mpa; and finally, maintaining the high temperature and removing the solvent under the condition that the vacuum degree is less than 0.085Mpa to obtain the silane coupling agent 1.

3. The silicone rubber according to claim 1, wherein silane coupling agent 2 is prepared by the following method: hydrogen-containing terminated dimethyl silicone oil and ethoxylated bisphenol A acrylate are mixed according to the proportion of 1-2: adding the mixture into a three-neck flask according to the molar ratio of 0.5-1, then adding toluene with the mass 1-3 times that of a reaction system and a Pt catalyst with the mass 8-16 ppm of the reaction system, reacting for 1-3 hours at the temperature of 60-90 ℃, then adding gamma-methacryloxypropyltrimethoxysilane with the same molar mass as that of the hydrogen-containing silicone oil,continuously reacting for 1-3 hours, adding activated carbon with the mass of 0.1-1% of that of the reaction system, stirring for 3-5 hours, filtering, and finally removing the solvent under the condition that the vacuum degree is less than 0.085Mpa at high temperature to obtain a silane coupling agent 2; the molecular formula of the hydrogen-containing end-capped dimethyl silicone oil is (HMe)₂SiO_0.5)₂(Me₂SiO_0.5)_mM is 8 to 200, the hydrogen content is 0.15 to 3mmol/g, and the viscosity is 15 to 50mPa.S at 25 ℃; the Pt catalyst is a vinyl siloxane complex of chloroplatinic acid, and the platinum content is 2000-6000 ppm.

4. The silicone rubber according to claim 1, wherein silane coupling agent 3 is prepared by the following method: adding a certain amount of side hydrogen-containing silicone oil into a three-neck flask, adding a mixture of propoxylated neopentyl glycol diacrylate and allyl glycidyl ether with the molar weight 1-1.5 times that of hydrogen contained in the hydrogen-containing silicone oil into the three-neck flask, wherein the molar ratio of the two monomers is 1-1.5, then adding toluene with the mass 1-3 times that of a reaction system and a Pt catalyst with the mass 8-16 ppm of the reaction system, reacting at 65-85 ℃ for 2-4 hours, adding active carbon with the mass 0.1-1% of the reaction system, stirring for 3-5 hours, filtering, and finally keeping the high temperature to remove the solvent under the condition that the vacuum degree is less than 0.085Mpa to obtain a silane coupling agent 3; the molecular formula of the side hydrogen-containing silicone oil is (Me)₃SiO_0.5)₂(Me₂SiO_0.5)_m(HMeSiO_0.5)_nM is 8-30, n is 25-40, hydrogen content is 0.25-9 mmol/g, and viscosity is 12-35 mPa.S at 25 ℃; the Pt catalyst is a vinyl siloxane complex of chloroplatinic acid, and the platinum content is 2000-6000 ppm.

5. The silicone gum according to claim 1, wherein the methyl vinyl MQ resin has a vinyl content of 0.25 to 0.5mmol/g, a viscosity at 25 ℃ of 3000 to 8000 mPa.S; the molecular formula of the methyl silicone oil is (Me)₃SiO_0.5)₂(Me₂SiO_0.5)_mA viscosity of 200 to 1000mPa.S at 25 ℃; the molecular formula of the hydrogen-containing silicone oilIs (Me)₃SiO_0.5)₂(Me₂SiO_0.5)_m(HMeSiO_0.5)_nM is 8 to 30, n is 25 to 40, the hydrogen content is 0.25 to 0.9mmol/g, and the viscosity at 25 ℃ is 30 to 75 mPa.S; the white carbon black has a specific surface area of 145-210 m²Hydrophobic white carbon black in a per gram ratio; the Pt catalyst is a vinyl siloxane complex of chloroplatinic acid, and the platinum content is 2000-6000 ppm; the inhibitor is one or more of 3-methyl-1-butine-3-alcohol, trimethyl-1-pentyne-3-alcohol, 3, 5-dimethyl-1-hexyne-3-alcohol and 1-ethynyl-1 cyclohexanol.

Technical Field

The invention relates to oil-resistant, high-temperature-resistant and low-volatile organic silica gel and a preparation method thereof, belonging to the field of organic silicon modification.

Technical Field

In the industrial production of the aviation industry, the automobile industry, the machinery manufacturing industry, the oil refining industry and the like, a large number of rubber sealing products capable of bearing the aging of media such as engine oil, lubricating oil, hydraulic oil and the like are generally needed. For example, in the assembly of an automobile engine or a transmission system, a liquid silicone rubber sealing gasket (FIPG) is required to replace the traditional solid gasket material, so that the design and production of the automobile meet the development requirements of the industries with light weight, small volume, high power, environmental protection and the like, and in the application occasions, the silicone rubber can be subjected to the continuous aging effect of hot engine oil, so that the strength and other mechanical properties of the silicone rubber are gradually reduced, and the service life of the material is influenced.

Along with the increase of the environmental protection requirement in recent years, the requirement on the volatile component of the glue is more and more strict. On one hand, the corrosion of volatile micromolecules to components is reduced, and on the other hand, the harm of the micromolecules emitted in the using process to human bodies is also reduced.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and discloses oil-resistant, high-temperature-resistant and low-volatile organic silica gel and a preparation method thereof. The silane coupling agent 1 adopted in the sealant has multiple advantages, and on one hand, the silane coupling agent 1 contains multiple ethoxy groups, so that the silane coupling agent can play a role of a coupling agent and a water absorbent, the content of moisture in a system is reduced, and the storage stability of a product is improved. On the other hand, the larger molecular weight can reduce the volatile component generated during the solidification of the glue, and meanwhile, the existence of the vinyl can connect the coupling agent into the glue body in a reaction mode and also can reduce the volatile component of the glue. The silane coupling agent 2 has higher molecular weight, and two adjacent benzene rings contained in the silane coupling agent can improve the cracking temperature of the glue at high temperature. In the molecule of the silane coupling agent 3, the contained ether chain molecules are filled among the polysiloxane molecular chains, so that the corrosion of oil molecules to colloids is effectively prevented.

The invention relates to an oil-resistant, high-temperature-resistant and low-volatile organic silica gel and a preparation method thereof, wherein the organic silica gel is a single-component gel, and the single-component gel comprises methyl vinyl MQ resin, methyl silicone oil, a silane coupling agent 1, a silane coupling agent 2, a silane coupling agent 3, hydrogen-containing silicone oil, white carbon black, a Pt catalyst, an inhibitor and black color paste according to the weight ratio of 20-35: 40-50: 0.5-3: 0.5-3: 0.5-3: 3-9: 1-6: 0.02-0.1: 0.02-0.1: 0.03-0.5 by weight.

The preparation method of the silane coupling agent 1 comprises the following steps:

dissolving pentaerythritol triacrylate and 8-18 ppm of tris (pentafluoro) phenylborane in a reaction system into toluene in a three-neck flask, and stirring for 15-35 min at room temperature to prepare a solution with the mass fraction of 25% -45%; slowly dripping triethoxysilane with the same molar mass as pentaerythritol triacrylate into the system, after dripping is finished, heating to 55-85 ℃, and reacting for 3-5 hours, wherein the negative pressure is less than 0.55 Mpa; and finally, maintaining the high temperature and removing the solvent under the condition that the vacuum degree is less than 0.085Mpa to obtain the silane coupling agent 1. The reaction formula is as follows:

the preparation method of the silane coupling agent 2 comprises the following steps:

hydrogen-containing terminated dimethyl silicone oil and ethoxylated bisphenol A acrylate are mixed according to the proportion of 1-2: adding the mixture into a three-neck flask according to a molar ratio of 0.5-1, then adding toluene with the mass 1-3 times that of a reaction system and a Pt catalyst with the mass 8-16 ppm that of the reaction system, reacting for 1-3 hours at 60-90 ℃, then adding gamma-methacryloxypropyltrimethoxysilane with the same molar mass as that of hydrogen-containing silicone oil, continuing to react for 1-3 hours, adding active carbon with the mass 0.1-1% that of the reaction system, stirring for 3-5 hours, filtering, and finally keeping the high temperature to remove the solvent under the condition that the vacuum degree is less than 0.085Mpa, thus obtaining the silane coupling agent 2. The hydrogen-containing terminated dimethyl silicone oilThe molecular formula is (HMe)₂SiO_0.5)₂(Me₂SiO_0.5)_mM is 8 to 200, the hydrogen content is 0.15 to 3mmol/g, and the viscosity is 15 to 50mPa.S at 25 ℃; the Pt catalyst is a vinyl siloxane complex of chloroplatinic acid, and the platinum content is 2000-6000 ppm.

The reaction formula is as follows:

a chain link structure is

The preparation method of the silane coupling agent 3 comprises the following steps:

(1) adding a certain amount of side hydrogen-containing silicone oil into a three-neck flask, adding a mixture of propoxylated neopentyl glycol diacrylate and allyl glycidyl ether with the molar weight 1-1.5 times that of hydrogen contained in the hydrogen-containing silicone oil into the three-neck flask, wherein the molar ratio of the two monomers is 1-1.5, then adding toluene with the mass 1-3 times that of a reaction system and a Pt catalyst with the mass 8-16 ppm of the reaction system, reacting at 65-85 ℃ for 2-4 hours, adding active carbon with the mass 0.1-1% of the reaction system, stirring for 3-5 hours, filtering, and finally keeping the high temperature to remove the solvent under the condition that the vacuum degree is less than 0.085Mpa to obtain the silane coupling agent 3. The molecular formula of the side hydrogen-containing silicone oil is (Me)₃SiO_0.5)₂(Me₂SiO_0.5)_m(HMeSiO_0.5)_nM is 8-30, n is 25-40, hydrogen content is 0.25-9 mmol/g, and viscosity is 12-35 mPa.S at 25 ℃; the Pt catalyst is a vinyl siloxane complex of chloroplatinic acid, and the platinum content is 2000-6000 ppm.

The reaction formula is as follows:

the technical scheme adopted by the invention is as follows:

(2) the methyl vinyl MQ resin has a vinyl content of 0.25-0.5 mmol/g and a viscosity of 3000-8000 mPa.S at 25 ℃;

(3) the molecular formula of the methyl silicone oil is (Me)₃SiO_0.5)₂(Me₂SiO_0.5)_mA viscosity of 200 to 1000mPa.S at 25 ℃;

(4) the molecular formula of the hydrogen-containing silicone oil is (Me)₃SiO_0.5)₂(Me₂SiO_0.5)_m(HMeSiO_0.5)_nM is 8-30, n is 25-40, hydrogen content is 0.25-9 mmol/g, and viscosity is 12-35 mPa.S at 25 ℃;

(5) the white carbon black has a specific surface area of 145-210 m²Hydrophobic white carbon black in a per gram ratio;

(6) the Pt catalyst is a vinyl siloxane complex of chloroplatinic acid, and the platinum content is 2000-6000 ppm;

(7) the inhibitor is one or more of 3-methyl-1-butine-3-alcohol, trimethyl-1-pentyne-3-alcohol, 3, 5-dimethyl-1-hexyne-3-alcohol and 1-ethynyl-1 cyclohexanol.

(8) The black color paste is a general color paste which is purchased from the market and is mixed by silicone oil and nano carbon black.

The silane coupling agent 1 adopted in the sealant prepared by the invention has a plurality of advantages, and on one hand, the silane coupling agent 1 contains a plurality of ethoxy groups, which can play the role of a coupling agent and a water absorbent, so that the content of water in a system is reduced, and the storage stability of the product is improved. On the other hand, the larger molecular weight can reduce the volatile component generated during the solidification of the glue, and meanwhile, the existence of the vinyl can connect the coupling agent into the glue body in a reaction mode and also can reduce the volatile component of the glue. The silane coupling agent 2 has higher molecular weight, and two adjacent benzene rings contained in the silane coupling agent can improve the cracking temperature of the glue at high temperature. In the molecule of the silane coupling agent 3, the contained ether chain molecules are filled among the polysiloxane molecular chains, so that the corrosion of oil molecules to colloids is effectively prevented.

Detailed Description

59.6g of pentaerythritol triacrylate and 8ppm of tris (pentafluoro) phenylborane in a reaction system are dissolved in 238g of toluene in a 500mL three-neck flask, the mixture is stirred for 15min at room temperature, 32.86g of triethoxysilane is slowly dripped into the system, after the dripping is finished, the temperature is raised to 55 ℃, the negative pressure is less than 0.55MPa, the reaction is carried out for 3.5h, and finally the solvent is removed under the condition that the vacuum degree is less than 0.085MPa at 120 ℃ to obtain the silane coupling agent 1.

66.2g of hydrogen-containing endcapped dimethyl silicone oil ((HMe)₂SiO_0.5)₂(Me₂SiO_0.5)_mM-8, hydrogen content 3mmol/g, viscosity 15mpa.s at 25 ℃), 21.23g of ethoxylated bisphenol a acrylate was added to a 500mL three-necked flask, followed by addition of 218g of toluene and 10ppm of Pt catalyst of the reaction system, reaction was carried out at 60 ℃ for 3 hours, addition of gamma-methacryloxypropyl trimethoxysilane and 49.6g of gamma-methacryloxypropyl trimethoxysilane, reaction was continued for 3 hours, addition of 1.4g of activated carbon, stirring for 4 hours, filtration was carried out, and finally the solvent was removed at 120 ℃ under a vacuum of less than 0.085Mpa to obtain silane coupling agent 2.

33.72g of pendant hydrogen-containing silicone oil ((Me)₃SiO_0.5)₂(Me₂SiO_0.5)_m(HMeSiO_0.5)_nM-30, n-25, a hydrogen content of 8.9mmol/g, and a viscosity of 20mpa.s at 25 ℃) was charged into a 500mL three-necked flask, a mixture of 49.26g of propoxylated neopentyl glycol diacrylate and 17.1g of allyl glycidyl ether was further charged into the three-necked flask, followed by addition of toluene in an amount 3 times the mass of the reaction system and a Pt catalyst in an amount of 10ppm of the reaction system, reaction at 70 ℃ for 4 hours, addition of 1g of activated carbon, stirring for 4 hours, filtration, and finally removal of the solvent at 120 ℃ under a vacuum of less than 0.085Mpa to obtain the silane coupling agent 3.