CN114133745B - Heat-resistant agent, high-temperature-resistant silicon rubber and preparation method thereof - Google Patents
Heat-resistant agent, high-temperature-resistant silicon rubber and preparation method thereof Download PDFInfo
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- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
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Abstract
The invention relates to the technical field of silicon rubber, and particularly relates to a heat-resistant agent which comprises, by mass, 2-10% of yttrium oxide, 3-15% of zirconium oxide, 25-40% of cerium oxide, 50% of raw methyl vinyl silicon rubber and 5-18% of titanium oxide. The invention also relates to high-temperature-resistant silicon rubber, and the preparation raw materials of the high-temperature-resistant silicon rubber comprise methyl vinyl silicone rubber raw rubber and the heat-resistant agent. The novel heat-resistant agent disclosed by the invention has good dispersibility in the silicone rubber, not only retains the original performance of the silicone rubber, but also has good elasticity and mechanical properties after the silicone rubber is aged, can be normally used at a high temperature of 350 ℃, meets the use requirements under certain harsh conditions, and widens the application field.
Description
Technical Field
The invention relates to the technical field of silicone rubber, and particularly relates to a heat-resistant agent, high-temperature-resistant silicone rubber and a preparation method thereof.
Background
The main chain of silicone rubber is composed of Si-O-Si bonds, which is one of the most important products of polysiloxane, and the silicone rubber has excellent heat resistance, cold resistance, oil resistance, chemical reagent resistance, radiation resistance, water vapor resistance, air permeability and the like, and is widely applied to industries such as aviation, aerospace, electrical, automobile, machinery and the like, medical treatment, health care, daily life and other fields.
The heat resistance of the silicone rubber is superior to that of organic rubber, good physical and mechanical properties can be kept at 150 ℃, the continuous time is more than 1000h at 200 ℃, but the silicone rubber is easy to embrittle and break at 350 ℃. With the development of science and technology, the technical field of silicone rubber has higher and higher requirements on the high temperature resistance of silicone rubber, but at present, silicone rubber can only be used for a short time at the temperature of more than 300 ℃, and the improvement of the high temperature resistance of silicone rubber is necessary in order to widen the application range of silicone rubber. The heat resistance of the silicon rubber is related to the type of raw rubber, the type and the using amount of a filler, a vulcanizing agent, a heat-resistant additive and the like. The addition of high temperature resistant additives is a common method for improving the high temperature aging resistance of silicone rubber.
The commonly used heat-resistant additive is mainly metal oxide which can keep good performance of the silicon rubber in a certain temperature range (lower than 350 ℃), but the silicon rubber can generate main chain fracture or side group oxidation in a range beyond the temperature range, the mechanical performance is reduced, and the compatibility of the heat-resistant agent and the silicon rubber is poor, so that the performance is influenced. The silicone resin can improve the temperature resistance of the silicone rubber, but the improvement is limited, and the mechanical properties such as hardness and the like are adversely affected. The heat resistance of the silicone rubber can be improved to a certain extent by introducing phenyl crude rubber, but the application is limited due to high price, CN 111909525A adopts diphenyl silanediol to replace a common structural control agent, and methyl phenyl vinyl silicone oil is added, the retention rate is 45.6% after aging at 300 ℃ for 3d, the temperature resistance level is insufficient, and the high-temperature elasticity is easy to lose. CN109867965A adopts boron heat-resistant agent, studies the aging condition of silicone rubber under high temperature, but the mass loss is larger. CN111073057B adopts nano zirconium hydroxide, nano yttrium oxide and hexaphenylcyclotrisilazane to match, and the mass loss is large after aging.
Therefore, it is required to provide a novel heat resistant agent for improving the high temperature resistance of silicone rubber.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a heat-resistant agent which can enable silicone rubber to show excellent high-temperature resistance at 350 ℃.
The other purpose of the invention is to provide a high temperature resistant silicone rubber, which still has certain elasticity and mechanical property after aging at 350 ℃ for 5 hours, has good high temperature resistance, and can be applied under high temperature conditions in the fields of automobiles, household appliances, aviation and the like.
The basic concept of the technical scheme adopted by the invention is as follows:
a heat-resistant agent comprises, by mass, 2-10% of yttrium oxide, 3-15% of zirconium oxide, 25-40% of cerium oxide, 50% of methyl vinyl silicone rubber crude rubber, and 5-18% of titanium oxide.
As a scheme, the heat-resistant agent is used for preparing silicone rubber resistant to the high temperature of 350 ℃.
The raw materials for preparing the high-temperature-resistant silicon rubber comprise raw methyl vinyl silicone rubber and the heat-resistant agent.
As a scheme, the preparation raw materials of the high-temperature-resistant silicon rubber also comprise white carbon black, a structural control agent, an internal mold release agent and a vulcanizing agent.
As a scheme, the preparation raw materials of the high-temperature-resistant silicon rubber comprise the following components in parts by weight:
100 parts of raw methyl vinyl silicone rubber;
35-50 parts of white carbon black;
0.2-10 parts of a structural control agent;
0.5-10 parts of heat-resistant agent;
0.05-0.3 part of internal mold release agent;
1-3 parts of a vulcanizing agent.
As a scheme, the molar mass of the raw methyl vinyl silicone rubber is 500000-750000g/mol, and the content of vinyl is 0.05-1.0 percent in terms of molar percentage.
As a scheme, the white carbon black is fumed silica, and the specific surface area is 200-380m 2 Per gram of silica.
Optionally, the internal mold release agent is one or more of zinc stearate, calcium stearate, barium stearate, magnesium stearate, zinc laurate, magnesium laurate, palmitic acid, lauric acid and stearic acid.
Optionally, the vulcanizing agent is one of 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide, dicumyl peroxide, benzoyl peroxide, 2, 4-dichlorobenzoyl peroxide or platinum vulcanizing agent.
As a scheme, the structural control agent is one or more than two of hydroxy silicone oil, vinyl hydroxy silicone oil, diphenyl dihydroxy silicone oil, dimethyl dimethoxy silane, dimethyl diethoxy silane, methyl phenyl dimethoxy silane, methyl phenyl diethoxy silane, hexamethyl disilazane, vinyl silazane, vinyl trimethoxy silane and vinyl triethoxy silane.
Optionally, the purity of the methyl phenyl dimethoxy silane is more than or equal to 99 percent, and the refractive index (n) is 25 D) 1.469 +/-0.005 and the content of polychlorinated biphenyl is 0.
Optionally, the viscosity of the vinyl hydroxyl silicone oil (25 ℃), mm 2 S: less than or equal to 35, hydroxyl content: (mol%) is more than or equal to 6.0%, and the vinyl content: (mol%) 6.5-7.5.
The invention also relates to the application of the high-temperature-resistant silicon rubber in the high-temperature working conditions in the fields of automobiles, household appliances and aviation.
The invention also relates to a preparation method of the high-temperature-resistant silicon rubber, which comprises the following steps:
(1) Putting raw methyl vinyl silicone rubber, a structural control agent and an internal release agent into a kneading machine to obtain a first mixed material;
(2) Adding white carbon black into the first mixed material in batches, uniformly mixing at 100 ℃, and standing for 4-8 hours to obtain a second mixed material;
(3) And banburying the second mixed material for 2-5h under the conditions of 0.04-0.08 MPa and 120-170 ℃ to obtain mixed base rubber, mixing the mixed base rubber and the heat-resistant agent in any scheme under the condition that the temperature is less than or equal to 100 ℃, uniformly mixing, and discharging.
The invention has the following beneficial effects:
1. the novel heat-resistant agent can improve the thermal stability of the silicone rubber, inhibit the main chain cracking and side chain oxidation of the silicone rubber, improve the heat resistance of the silicone rubber at a high temperature of 350 ℃, and contribute to widening the application range of the silicone rubber.
2. The novel heat-resistant agent disclosed by the invention has good dispersibility in the silicone rubber, not only retains the original properties of the silicone rubber, but also has good elasticity and mechanical properties after the silicone rubber is aged, can be normally used at a high temperature of 350 ℃, meets the use requirements under certain harsh conditions, and widens the application field.
3. The high-temperature-resistant silicon rubber disclosed by the invention has the characteristics of certain elasticity, mechanical property and the like after being aged for 5 hours at 350 ℃, has good high-temperature resistance, and can be applied to the high-temperature conditions of the automobile field, household appliances, aviation and the like.
4. The silicon rubber adopts raw methyl vinyl silicon rubber as a matrix material, and the white carbon black is used as a reinforcing filler of the silicon rubber, and the structural control agent can be condensed with active hydroxyl of the white carbon black, so that the direct structuring of the white carbon black and the silicon rubber is inhibited, the gel content of the silicon rubber is reduced, and the processing performance of the silicon rubber is improved. The internal release agent increases the lubricity of the surface of the silicon rubber, is a direct functional substance between a product and a mould, and improves the release property. The vulcanizing agent enables linear molecules to form a three-dimensional net structure, and the mechanical property is improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
Fig. 1 is a graph showing the thermal weight loss properties of the silicone rubber prepared in comparative example 3.
Fig. 2 is a graph showing the thermal weight loss properties of the silicone rubber of example 3.
Detailed Description
The technical solutions of the present invention are described clearly and completely below, and it is obvious that the described embodiments are some, not all embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
In the following examples, "part" means "part by weight", and the unit of measurement of "part" or "part by weight" in the same example is uniform, and the idea of the embodiment defined by the specific unit of measurement is the same, and does not affect the feasibility of the embodiment.
In the case where not specifically mentioned, the term "%" means the content of vinyl groups as a molar percentage "mol%", and the term "%" in the heat-resistant agent as a weight percentage "w t%".
Example 1
100 parts of methyl vinyl silicone rubber raw rubber with the average molecular weight of 68.9 ten thousand and the average vinyl content of 0.168mol percent (wherein 65 parts of methyl vinyl silicone rubber raw rubber with the vinyl content of 0.05mol percent and the molecular weight of 70 ten thousand, 33 parts of methyl vinyl silicone rubber raw rubber with the vinyl content of 0.23mol percent and the molecular weight of 50 ten thousand, 2 parts of methyl vinyl silicone rubber raw rubber with the vinyl content of 3mol percent), 47 parts of gas phase white carbon black (XHG-300, zhejiang Kaiki synthetic materials Co., ltd.), 2.0 parts of hydroxyl silicone oil (the viscosity of 25 ℃ is 25 mm) 2 (s) hydroxyl group content 8.5wt%, 1.5 parts of hexamethyldisilazane (content. Gtoreq.99%), 1.5 parts of vinyl hydroxysilicone oil ((viscosity (25 ℃ C.)), mm) 2 S:35, hydroxyl group content: (mol%) 6.0, vinyl content: (mol%) 7.0)), 1.0 part of methyl phenyl dimethoxy silane (HY-PS-9116, hangzhou Yi science and technology product center) and 0.1 part of zinc stearate (Hangzhou grease chemical Co., ltd.) are kneaded, the components are discharged, the rubber material is divided into blocks, the blocks are kept still for 4 hours, then the blocks are put into a kneader to be heated to about 155 ℃ for high-temperature banburying, heat preservation is carried out, low-molecular substances are removed, and the rubber material is cooled to be below 100 ℃.
4 parts of a heat-resistant agent (2% yttrium oxide, 5% zirconium oxide, 25% cerium oxide, 50% raw methyl vinyl silicone rubber and 18% by weight of TiO) 2 ) Continuously kneading (cooling water is needed to be fed, the temperature can not exceed 100 ℃) for 30min, then discharging to obtain the high temperature resistant silicon rubber, cutting the rubber material into sheet rubber materials, cooling for more than 30min, performing open milling, filtering, weighing and packaging to obtain the high temperature resistant silicon rubber finished product.
Taking 100 parts of the finished high-temperature-resistant silicon rubber, mixing and dispersing 1 part of 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide by using a 150mm open mill to prepare a curable silicon rubber composition, carrying out plate vulcanization on the curable silicon rubber composition at 170 ℃ for 10min to obtain first-stage vulcanization, and simultaneously carrying out vulcanization at 200 ℃ for 2h to obtain second-stage vulcanization, and detecting the mechanical properties of the curable silicon rubber composition.
Example 2
100 parts of methyl vinyl silicone rubber raw rubber with the average molecular weight of 68.2 ten thousand and the average vinyl content of 0.226mol percent (wherein 50 parts of methyl vinyl silicone rubber raw rubber with the vinyl content of 68 ten thousand and the average vinyl content of 0.08mol percent, 48.2 parts of methyl vinyl silicone rubber raw rubber with the vinyl content of 70 ten thousand and 1.8 parts of methyl vinyl silicone rubber raw rubber with the vinyl content of 5mol percent and the average molecular weight of 50 ten thousand), 40 parts of fumed silica (HL-200, yichang silicon-rich material Limited company), 0.5 part of hydroxyl silicone oil (the viscosity of 25mm at the temperature of 25℃ is 25 mm) 2 (s) hydroxyl group content 8.5wt%, 0.6 part of hexamethyldisilazane (content. Gtoreq.99%), 2.0 parts of vinylhydroxysilicone oil ((viscosity (25 ℃ C.)), mm) 2 S:35, hydroxyl group content: (mol%) 6.0, vinyl content: (mol%) 7.0)), 2.0 parts of methyl phenyl diethoxy silane (Hubei xing Hengshi science and technology limited), 0.08 part of stearic acid (Hangzhou grease chemical limited), kneading all the components, discharging glue, dividing the glue into blocks, standing for 4 hours, then putting the blocks into a kneader, heating to about 165 ℃ for high-temperature banburying, preserving heat, removing low molecules, and cooling the glue to below 100 ℃.
5.5 parts of a heat-resistant agent (5% yttrium oxide, 4% zirconium oxide, 30% cerium oxide, 50% raw methyl vinyl silicone rubber and 11% TiO) was added 2 ) Continuously kneading (cooling water is needed, the temperature cannot exceed 100 ℃) for 30min, discharging to obtain high-temperature-resistant silicon rubber, dividing the rubber into flaky rubber, cooling for more than 30min, milling, filtering, weighing and packaging to obtain a high-temperature-resistant silicon rubber finished product.
Taking 100 parts of the finished high-temperature-resistant silicon rubber product, mixing and dispersing 1 part of 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide by using a 150mm open mill to prepare a curable silicon rubber composition, carrying out plate vulcanization on the curable silicon rubber composition at 170 ℃ for 10min to obtain first-stage vulcanization, simultaneously carrying out vulcanization after 2h at 200 ℃ to obtain second-stage vulcanization, and detecting the mechanical properties of the curable silicon rubber composition.
Example 3
100 parts of raw methyl vinyl silicone rubber having an average molecular weight of 68.5 ten thousand and an average vinyl content of 0.235mol% (59 parts of raw methyl vinyl silicone rubber having a vinyl content of 0.05mol% and having a molecular weight of 70 ten thousand, 37 parts of raw methyl vinyl silicone rubber having a vinyl content of 0.23mol% and having a vinyl content of 3mol% and having a molecular weight of 50 ten thousand), 42 parts of fumed silica (Deshan QS-25, japan Deshan corporation), 1.0 part of hydroxy silicone oil (viscosity of 25mm at 25 ℃ C.) were added 2 (s) hydroxyl group content 8.5wt%, 0.9 part of hexamethyldisilazane (content. Gtoreq.99%), and 1.0 part of vinylhydroxysilicone oil ((viscosity (25 ℃ C.)), mm) 2 S:35, hydroxyl group content: (mol%) 6.0, vinyl content in mole percent: (mol%) 7.0)), 1.5 parts of methyl phenyl dimethoxy silane (HY-PS-9116, hangzhou Yi science and technology center) and 0.1 part of calcium stearate (Hangzhou grease chemical Co., ltd.) are kneaded, the components are separated, the mixture is divided into blocks, the blocks are kept still for 4 hours, then the blocks are put into a kneader to be heated to about 150 ℃ for high-temperature banburying, heat preservation is carried out, low molecules are removed, and the blocks are cooled to be below 100 ℃.
Adding 5 parts of heat resistant agent (4% yttrium oxide, 6% zirconium oxide, 27% cerium oxide, 50% methyl vinyl silicone rubber crude rubber and 13% TiO% 2 ). Continuously kneading (cooling water is needed, the temperature cannot exceed 100 ℃) for 30min, discharging to obtain high-temperature-resistant silicon rubber, dividing the rubber into flaky rubber, cooling for more than 30min, milling, filtering, weighing and packaging to obtain a high-temperature-resistant silicon rubber finished product.
Taking 100 parts of the finished high-temperature-resistant silicon rubber, mixing and dispersing 1 part of 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide by using a 150mm open mill to prepare a curable silicon rubber composition, carrying out plate vulcanization on the curable silicon rubber composition at 170 ℃ for 10min to obtain first-stage vulcanization, and simultaneously carrying out vulcanization at 200 ℃ for 2h to obtain second-stage vulcanization, and detecting the mechanical properties of the curable silicon rubber composition.
Example 4
The average molecular weight is 67.6 ten thousand, and the average vinyl content is 0.20m100 parts of ol% methyl vinyl silicone rubber raw rubber (57 parts of methyl vinyl silicone rubber raw rubber with the molecular weight of 70 ten thousand and the vinyl content of 0.08mol%, 40 parts of methyl vinyl silicone rubber raw rubber with the molecular weight of 65 ten thousand and the vinyl content of 0.16mol%, 3 parts of methyl vinyl silicone rubber raw rubber with the molecular weight of 50 ten thousand and the vinyl content of 3 mol%), 41 parts of fumed silica (HL-300, yichanghui silicon-rich Material Co., ltd.), 1.0 part of hydroxyl silicone oil (the viscosity at 25 ℃ is 25 mm) 2 (s) hydroxyl group content 8.5wt%, 1.2 parts of hexamethyldisilazane (content. Gtoreq.99%), and 1.5 parts of vinylhydroxysilicone oil ((viscosity (25 ℃ C.)), mm) 2 S:35, hydroxyl group content: (mol%) 6.0, vinyl content: (mol%) 7.0)), 1.0 part of methyl phenyl diethoxysilane (Hubei xing Hengheng science and technology Co., ltd.) and 0.15 part of polyethylene glycol distearate (Hemington, modest and chemical Co., ltd.) are mixed, the mixture is discharged, the mixture is divided into blocks, the blocks are kept still for 4 hours, then the blocks are put into a kneader to be heated to about 160 ℃ for high-temperature mixing, heat preservation is carried out, low molecules are removed, and the mixture is cooled to below 100 ℃.
6 parts of a heat-resistant agent (2% yttrium oxide, 5% zirconium oxide, 30% cerium oxide, 50% methyl vinyl green rubber and 13% by weight of TiO) 2 ) Continuously kneading (cooling water is needed, the temperature cannot exceed 100 ℃) for 30min, discharging, cutting the rubber material into sheet-shaped rubber materials to obtain the high-temperature-resistant silicon rubber, cooling for more than 30min, milling, filtering, weighing and packaging to obtain the high-temperature-resistant silicon rubber finished product.
Taking 100 parts of the finished high-temperature-resistant silicon rubber product, mixing and dispersing 1 part of 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide by using a 150mm open mill to prepare a curable silicon rubber composition, carrying out plate vulcanization on the curable silicon rubber composition at 170 ℃ for 10min to obtain first-stage vulcanization, simultaneously carrying out vulcanization after 2h at 200 ℃ to obtain second-stage vulcanization, and detecting the mechanical properties of the curable silicon rubber composition.
Example 5
100 parts of methyl vinyl silicone rubber raw rubber with the average molecular weight of 70.2 ten thousand and the average vinyl content of 0.203mol percent (55 parts of methyl vinyl silicone rubber raw rubber with the vinyl content of 0.08mol percent and the molecular weight of 73 ten thousand and vinyl with the molecular weight of 65 ten thousand)43 parts of methyl vinyl silicone rubber raw rubber with the content of 0.23mol%, 2 parts of methyl vinyl silicone rubber raw rubber with the molecular weight of 55 ten thousand and the vinyl content of 3mol%, 45 parts of fumed silica (XHG-200, zhejiang Kaihua synthetic materials Co., ltd.), 0.8 part of hydroxyl silicone oil (the viscosity at 25 ℃ is 25 mm) 2 (s) hydroxyl group content 8.5wt%, 0.8 part of hexamethyldisilazane (content. Gtoreq.99%), 0.8 part of vinyl hydroxysilicone oil ((viscosity (25 ℃ C.)), mm) 2 S:35, hydroxyl group content: (mol%) 6.0, vinyl content: (mol%) 7.0)), 1.0 part of methyl phenyl dimethoxy silane (HY-PS-9116, hangye science and technology center) and 0.08 part of palmitic acid (Nanjing Todede chemical technology Co., ltd.) through the steps of kneading the components, discharging the rubber, dividing the rubber into blocks, standing for 4 hours, putting the blocks into a kneader, heating to about 170 ℃ for banburying at high temperature, keeping the temperature, removing low molecules, and cooling the rubber to below 100 ℃.
6.5 parts of a heat-resistant agent (3% yttrium oxide, 4% zirconium oxide, 33% cerium oxide, 50% raw methyl vinyl silicone rubber and 10% TiO) was added 2 ) Continuously kneading (cooling water is needed, the temperature cannot exceed 100 ℃) for 30min, discharging to obtain high-temperature-resistant silicon rubber, dividing the rubber into flaky rubber, cooling for more than 30min, milling, filtering, weighing and packaging to obtain a high-temperature-resistant silicon rubber finished product.
Taking 100 parts of the finished high-temperature-resistant silicon rubber product, mixing and dispersing 1 part of 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide by using a 150mm open mill to prepare a curable silicon rubber composition, carrying out plate vulcanization on the curable silicon rubber composition at 170 ℃ for 10min to obtain first-stage vulcanization, simultaneously carrying out vulcanization after 2h at 200 ℃ to obtain second-stage vulcanization, and detecting the mechanical properties of the curable silicon rubber composition.
Example 6
100 parts of raw methyl vinyl silicone rubber with the average molecular weight of 69.3 ten thousand and the average vinyl content of 0.217mol percent (wherein 56 parts of raw methyl vinyl silicone rubber with the average molecular weight of 68 ten thousand and the vinyl content of 0.08mol percent, 41 parts of raw methyl vinyl silicone rubber with the average molecular weight of 72 ten thousand and the vinyl content of 0.20mol percent and 3 parts of raw methyl vinyl silicone rubber with the average molecular weight of 55 ten thousand and the vinyl content of 3mol percent) and 40 parts of fumed silica(De shan QS-30, manufactured by Deshan Japan K.K.), 1.8 parts of a hydroxy silicone oil (viscosity at 25 ℃ C. Is 25 mm) 2 (s) hydroxyl group content 8.5% (mass content)), 1.0 part of hexamethyldisilazane (content. Gtoreq.99%), and 1.2 parts of vinylhydroxysilicone oil (viscosity (25 ℃ C.), mm 2 S:35, hydroxyl group content: (mol%) is more than or equal to 6.0, and the vinyl content: (mol%) 7.0)), 0.8 part of methyl phenyl dimethoxy silane (HY-PS-9116, hangYi science and technology product center), 0.1 part of lauric acid (Nanjing Dongde chemical technology Co., ltd.), kneading the components, discharging the glue, cutting the glue into blocks, standing for 4h, then putting into a kneader, heating to about 155 ℃ for high-temperature banburying, preserving heat, removing low molecules, and cooling the glue to below 100 ℃.
6.5 parts of a heat-resistant agent (2% yttrium oxide, 5% zirconium oxide, 34% cerium oxide, 50% raw methyl vinyl silicone rubber and 9% TiO) was added 2 ). Continuously kneading (cooling water is needed to be fed, the temperature can not exceed 100 ℃) for 30min, then discharging to obtain the high temperature resistant silicon rubber, cutting the rubber material into sheet rubber materials, cooling for more than 30min, performing open milling, filtering, weighing and packaging to obtain the high temperature resistant silicon rubber finished product.
Taking 100 parts of the finished high-temperature-resistant silicon rubber, mixing and dispersing 1 part of 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide by using a 150mm open mill to prepare a curable silicon rubber composition, carrying out plate vulcanization on the curable silicon rubber composition at 170 ℃ for 10min to obtain first-stage vulcanization, and simultaneously carrying out vulcanization at 200 ℃ for 2h to obtain second-stage vulcanization, and detecting the mechanical properties of the curable silicon rubber composition.
Example 7
The difference from example 6 is that: 6.0 parts of a heat-resistant agent (7% yttrium oxide, 3% zirconium oxide, 28% cerium oxide, 50% raw methyl vinyl silicone rubber and 12% TiO) was added 2 )。
Example 8
The difference from example 3 is that: adding 6.0 parts of heat resistant agent (5% yttrium oxide, 5% zirconium oxide, 30% cerium oxide, 50% methyl vinyl silicone rubber crude rubber and 10% TiO% 2 )。
Example 9
The difference from example 1 is that: 4 parts of a heat-resistant agent (15% yttrium oxide, 11% zirconium oxide, 20% cerium oxide, 50% raw methyl vinyl silicone rubber and 4% TiO2) was added.
Example 10
The difference from example 1 is that: 4 parts of heat-resistant agent (11% yttrium oxide, 2% zirconium oxide, 27% cerium oxide, 50% raw methyl vinyl silicone rubber and 10% TiO2) was added.
Comparative example 1
The difference from example 3 is that: the heat-resistant agent was replaced with commercial WACKER H6, and the rest was the same as in example 3.
Comparative example 2
The difference from example 3 is that: the heat-resistant agent was replaced with a commercially available heat-resistant agent WACKER H0, and the rest was the same as in example 3.
Comparative example 3
The difference from example 3 is that: the heat-resistant agent was replaced with 4.0 parts of a commercially available heat-resistant agent WACKER H6 and 1.0 part of a commercially available heat-resistant agent WACKER H0, and the rest was the same as in example 3.
Test example
According to the national standard, the Shore hardness, the tensile strength, the elongation at break, the tearing strength, the rebound resilience and the hot air aging performance of the high-temperature-resistant silicon rubber prepared in the embodiment and the comparative example of the invention after the same vulcanization treatment are respectively tested.
The specific test method is as follows:
the Shore hardness is tested according to the GB/T531.1-2008 standard;
testing the tensile strength and the elongation at break according to GB/T528-2009 standard;
the tearing strength is tested according to the GB/T529-2008 standard;
the rebound is tested according to GB/T1681-2009 standard;
hot air ageing was according to GB/T3512-2004.
The experimental data obtained are found in the secondary vulcanization and hot air aging properties of the silicone rubbers of tables 1-2 below.
TABLE 1
TABLE 2
As can be seen from tables 1-2, in comparative example 1, the heat-resistant agent was replaced with commercially available WACKER H6; comparative example 2 compared to example 3, the commercial WACKER H0 was used instead of commercial WACKER H0, and comparative example 3 compared to example 3, the hardness of the silicone rubber of comparative examples 1-3 after hot air aging at 350 ℃ for 5H was significantly increased due to oxidation of the side chain groups of the silicone rubber, which increased the crosslinking points and caused an increase in hardness, and the sample after aging was significantly embrittled and lost mechanical properties.
Examples 1-8 using the novel heat resistant agent of the present invention, silicone rubber had a low mass loss of about 10% after aging in hot air at 350 ℃ for 5 hours, and still maintained good mechanical properties. And the mass loss of the silicone rubber added with the commercial heat-resistant agent is slightly large, and the rubber material is brittle and broken and loses the mechanical property.
In examples 9 and 10, the heat-resistant agent components were not in the preferred ratios described in the present invention, and in example 9, none of yttrium oxide, cerium oxide, and titanium oxide was in the preferred ranges described in the present invention, and the tensile strength was significantly reduced after aging at 350 ℃ for 5 hours, as compared with example 1. In example 10, the yttria and zirconia were out of range and the tensile strength was slightly reduced after aging at 350 ℃ for 5 hours.
As an example, the results of the thermal weight loss performance test of inventive example 3 and comparative example 3 are given herein.
FIG. 1 is a graph of the weight loss on heating of comparative example 3 (with 4 parts H6 and 1 part H0 heat resistance added) silicone rubber, with a 5% weight loss temperature of 420.57 ℃ and an epitaxy onset temperature of 441.83 ℃. FIG. 2 is a graph showing the thermogravimetric curves of silicone rubber of example 3 (5 parts of the novel heat-resistant agent added) at a temperature of 446.76 ℃ for 5% weight loss and 476.83 ℃ for the onset of epitaxy. And in combination with tables 1-2, the mechanical properties of the silicone rubber added with the heat-resistant agents H6 and H0 in comparative example 3 and the novel heat-resistant agent in example 3 are better, and the embrittlement of the added heat-resistant agents H6 and H0 loses the service performance after the aging in hot air at 350 ℃ for 5H.
Therefore, the novel heat-resistant agent disclosed by the invention not only has the characteristic of better resistance to the high temperature of 350 ℃, but also ensures the mechanical property of the silicon rubber.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (13)
1. A heat-resistant agent is used for preparing silicon rubber resistant to high temperature of 350 ℃, and comprises 2-10% of yttrium oxide, 3-15% of zirconium oxide, 25-40% of cerium oxide, 50% of methyl vinyl silicon rubber crude rubber and 5-18% of titanium oxide in percentage by mass.
2. The high-temperature-resistant silicon rubber is prepared from raw materials of methyl vinyl silicone rubber and the heat-resistant agent as claimed in claim 1.
3. The high temperature resistant silicone rubber according to claim 2, wherein the raw materials for preparing the high temperature resistant silicone rubber further comprise white carbon black, a structural control agent, an internal mold release agent and a vulcanizing agent.
4. The high-temperature-resistant silicone rubber according to claim 3, wherein the preparation raw materials of the high-temperature-resistant silicone rubber comprise the following components in parts by weight:
100 parts of raw methyl vinyl silicone rubber;
35-50 parts of white carbon black;
0.2-10 parts of a structural control agent;
0.5-10 parts of heat-resistant agent;
0.05-0.3 part of internal mold release agent;
1-3 parts of a vulcanizing agent.
5. The high-temperature-resistant silicone rubber according to any one of claims 2 to 4, wherein the raw methyl vinyl silicone rubber has a molar mass of 500000 to 750000g/mol and a vinyl content of 0.05 to 1.0% in terms of mole percentage.
6. The high-temperature-resistant silicone rubber according to claim 3 or 4, wherein the white carbon black is fumed silica having a specific surface area of 200-380m 2 Per gram of silica.
7. The high-temperature-resistant silicone rubber according to claim 6, wherein the internal mold release agent is one or more of zinc stearate, calcium stearate, barium stearate, magnesium stearate, zinc laurate, magnesium laurate, palmitic acid, lauric acid, and stearic acid.
8. The high temperature resistant silicone rubber of claim 6, wherein the vulcanizing agent is one of 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide, dicumyl peroxide, benzoyl peroxide, 2, 4-dichlorobenzoyl peroxide or platinum vulcanizing agent.
9. The high temperature resistant silicone rubber of claim 3 or 4, wherein the structural control agent is one or more of hydroxy silicone oil, vinyl hydroxy silicone oil, diphenyl dihydroxy silicone oil, dimethyl dimethoxy silane, dimethyl diethoxy silane, methyl phenyl dimethoxy silane, methyl phenyl diethoxy silane, hexamethyl disilazane, vinyl silazane, vinyl trimethoxy silane, and vinyl triethoxy silane.
10. The high-temperature-resistant silicone rubber as recited in claim 9, wherein the purity of the methylphenyldimethoxysilane is not less than 99%, and the refractive index (n) is 25 D) 1.469 +/-0.005 and the content of polychlorinated biphenylIs 0.
11. The high temperature resistant silicone rubber according to claim 9, wherein the viscosity of the vinylhydroxysilicone oil is (25 ℃) in mm 2 S: less than or equal to 35, hydroxyl content: (mol%) is more than or equal to 6.0%, and the vinyl content is as follows: (mol%) 6.5-7.5.
12. Use of the high temperature resistant silicone rubber according to any one of claims 2 to 11 in high temperature conditions in the automotive, household appliance and aerospace fields.
13. A preparation method of high-temperature-resistant silicon rubber comprises the following steps:
(1) Putting raw methyl vinyl silicone rubber, a structural control agent and an internal release agent into a kneading machine to obtain a first mixed material;
(2) Adding white carbon black into the first mixed material in batches, uniformly mixing at 100 ℃, and standing for 4-8 hours to obtain a second mixed material;
(3) Banburying the second mixed material for 2-5h under the conditions of 0.04-0.08 MPa and 120-170 ℃ to obtain mixed base rubber, mixing the mixed base rubber and the heat-resistant agent of claim 1 under the condition that the temperature is less than or equal to 100 ℃, uniformly mixing and discharging.
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