CN112480683A - Halogen-free flame-retardant heat-resistant silicone rubber composite material and preparation method thereof - Google Patents
Halogen-free flame-retardant heat-resistant silicone rubber composite material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of silicone rubber, in particular to a halogen-free flame-retardant heat-resistant silicone rubber composite material and a preparation method thereof. The halogen-free flame-retardant heat-resistant silicone rubber composite material comprises the following raw materials in percentage by mass: 20% -50% of silicon rubber; 10 to 30 percent of white carbon black; 10% -50% of flame retardant; 5% -40% of heat-resistant agent; 1-10% of processing aid. The high-performance halogen-free flame-retardant heat-resistant silicon rubber material prepared by the invention not only has excellent physical and mechanical properties, but also has excellent heat resistance, the thermal decomposition temperature of the high-performance halogen-free flame-retardant heat-resistant silicon rubber material is 50-100 ℃ higher than that of a common silicon rubber material, and the application requirements of special industries such as military industry, high-speed rail and the like can be met. The invention has simple process route and stable product quality, and is suitable for industrial production.
Description
Technical Field
The invention relates to the technical field of silicone rubber, in particular to a halogen-free flame-retardant heat-resistant silicone rubber composite material and a preparation method thereof.
Background
The silicone rubber material with excellent physical and mechanical properties, electrical properties and chemical corrosion resistance is widely applied to various fields of social life, and especially plays an important role in some special fields. The performance of the silicon rubber material can meet different performance requirements through the design of a formula, but most products cannot meet the special performance requirements in the fields of war industry, aerospace, high-speed traffic and the like due to the weak foundation of the silicon rubber industry in China, need to be imported in large quantity, and are subject to foreign technical blockages. Among them, high-performance halogen-free flame-retardant heat-resistant silicone rubber materials are one of them.
The flame-retardant modification of the silicone rubber is always a hot point of domestic and foreign research, and the existing silicone rubber material with high flame-retardant performance is expensive or has low comprehensive performance, so that the application requirements of high-end fields are difficult to meet. In the prior art, expensive platinum catalysts, polysilsesquioxane flame retardants and other substances are adopted, the product has good flame retardant performance (up to UL 94V-0 level), but the material mechanical property is poor, the cost is high, although the addition amount of platinum compounds is very small, even if the addition amount is only 1-500 ppm, the price of noble metal platinum compounds is high, the cost of each kilogram of mixed silicon rubber needs to be increased by more than 10 yuan, the platinum compound manufacturing process is complex, and the pollution in the manufacturing process is serious. In addition, in the prior art, aluminum hydroxide, melamine cyanurate and zinc borate are mainly used as flame retardants, the flame retardant performance of the product can reach UL 94V-0 level, the cost is low, but the mechanical property is poor, the tensile strength is only about 4MPa, and the elongation at break is 400-480%. In addition, in the prior art, the coating treatment of the potassium melamine phosphate is used as a flame retardant, and the product has good physical and mechanical properties and flame retardant performance, the tensile strength is 8.5MPa, the tear strength is 23kN/m, and the oxygen index is 36%. However, these patents only focus on the flame retardant properties of the material and do not relate to the heat resistance of the material.
In addition, a plurality of compound flame retardants and heat-resistant agents are added, so that the material has good physical and mechanical properties, flame retardant properties and heat resistance, but the preparation method is very complex, the compound flame retardants need to undergo multi-step chemical reactions, the raw materials are expensive, rubber materials of A, B two components need to be prepared in advance and can be used after being uniformly mixed in a ratio of 1:1 during use, and the product stability is poor.
Disclosure of Invention
In view of the above-mentioned disadvantages of the prior art, the present invention aims to provide a halogen-free flame retardant heat-resistant silicone rubber composite material, a preparation method and a use thereof, which are used for solving the problems in the prior art.
In order to achieve the above objects and other related objects, one aspect of the present invention provides a halogen-free flame retardant heat resistant silicone rubber composite material, which comprises the following components in percentage by mass:
in some embodiments of the invention, the halogen-free flame-retardant heat-resistant silicone rubber composite material comprises the following components in percentage by mass:
in some embodiments of the invention, the silicone rubber is selected from the group consisting of methyl vinyl silicone rubber, phenyl silicone rubber, and combinations of one or more thereof.
In some embodiments of the invention, the methyl vinyl silicone rubber has a vinyl content of 0.04% to 1.6%; the molecular weight of the methyl vinyl silicone rubber is 50-100 ten thousand.
In some embodiments of the present invention, the methyl vinyl silicone rubber comprises a methyl vinyl silicone rubber having a vinyl content of 0.04% to 0.06% and a methyl vinyl silicone rubber having a vinyl content of 1.2% to 1.6%.
In some embodiments of the present invention, the phenyl silicone rubber has a molecular weight of 40 to 80 ten thousand; the phenyl silicone rubber contains 5% -40% of phenyl.
In some embodiments of the present invention, the white carbon black is selected from fumed silica.
In some embodiments of the invention, the flame retardant is selected from the group consisting of surface modified aluminum hydroxide, aluminum hypophosphite, and combinations thereof.
In some embodiments of the invention, the heat resistant agent is selected from calcined black iron oxide and/or nano titanium dioxide.
In some embodiments of the invention, the processing aid is selected from the group consisting of one or more of a hydroxy silicone oil, a silane coupling agent, and an antioxidant.
In another aspect, the invention provides a preparation method of the halogen-free flame-retardant heat-resistant silicone rubber composite material, comprising the following steps: the silicon rubber flame retardant is prepared by mixing silicon rubber, white carbon black, a flame retardant, a heat-resistant agent and a processing aid.
The invention also provides application of the halogen-free flame-retardant heat-resistant silicone rubber composite material in the field of silicone rubber preparation.
In another aspect, the invention provides a silicone rubber, which comprises the halogen-free flame-retardant heat-resistant silicone rubber composite material.
Compared with the prior art, the invention has the beneficial effects that:
the high-performance halogen-free flame-retardant heat-resistant silicon rubber material prepared by the method has excellent physical and mechanical properties and excellent heat resistance, has a thermal decomposition temperature 50-100 ℃ higher than that of a common silicon rubber material, and can meet the application requirements of special industries such as military industry, high-speed rail and the like. The invention has simple process route and stable product quality, and is suitable for industrial production.
Detailed Description
The inventor provides a halogen-free flame-retardant heat-resistant silicone rubber composite material, a preparation method and application thereof through a large number of exploration experiments. The excellent comprehensive performance of the composite material is realized by blending different types of silicon rubber combinations with different vinyl contents and adding efficient flame retardant and heat-resistant agent. Wherein, the combination of different types and vinyl content of silicone rubber can realize good processing performance and higher original mechanical performance; the high-efficiency flame retardant can meet the flame-retardant requirement of the material under the condition of low addition amount, and the low addition amount can not cause great influence on the mechanical property of the material; the addition of the heat-resistant agent can greatly improve the decomposition temperature of the silicon rubber and delay the spontaneous combustion time, so that the material can meet the requirement of higher working temperature. On the basis of this, the present invention has been completed.
The invention provides a halogen-free flame-retardant heat-resistant silicone rubber composite material, which comprises the following raw materials of silicone rubber, white carbon black, a flame retardant, a heat-resistant agent and a processing aid.
In the halogen-free flame-retardant heat-resistant silicone rubber composite material provided by the invention, the raw materials can comprise 20-50% of silicone rubber in percentage by mass. In some embodiments, the mass percentage of the silicone rubber may also be 25% -40%; 20% -35%, 35% -50%; or 20% -30%, 30% -40%, or 40% -50%; 25% -45% and 30% -40%. For example, the silicone rubber is selected from one or more of methyl vinyl silicone rubber and phenyl silicone rubber.
The methyl vinyl silicone rubber has a vinyl content of 0.04% to 1.6%, and in some embodiments, the methyl vinyl silicone rubber has a vinyl content of, for example, 0.04% to 0.1%, 0.1% to 0.5%, 0.5% to 1.0%, or 1.0% to 1.6%; 0.04 to 0.06 percent; 1.2 to 1.6 percent and the like. The molecular weight of the methyl vinyl silicone rubber is 50-100 ten thousand. In some embodiments, the methyl vinyl silicone rubber has a molecular weight of 50 to 60 ten thousand; 60 to 70 ten thousand; 70-80 ten thousand; 80-90 ten thousand; or 90 to 100 million, etc.
In one embodiment, methylvinyl silicone rubbers with different vinyl contents can be selected for use in combination, for example, a low vinyl content methylvinyl silicone rubber can be mixed with a high vinyl content methylvinyl silicone rubber. Specifically, the methyl vinyl silicone rubber can comprise a mixture of methyl vinyl silicone rubber with a vinyl content of 0.04-0.06% and methyl vinyl silicone rubber with a vinyl content of 1.2-1.6%. More specifically, the low vinyl content methyl vinyl silicone rubber may be a methyl vinyl silicone rubber including a vinyl content of 0.04% to 0.05% or 0.05% to 0.06%. The content of vinyl with high vinyl content is 1.2 to 1.4 percent; 1.4% -1.6%; 1.2% -1.3%; 1.3% -1.4%; 1.4% -1.5%; 1.5% -1.6%; or 1.3 to 1.5 percent of methyl vinyl silicone rubber. The mass ratio of the two types of methyl vinyl silicone rubber with different vinyl contents can be 0.5-3: 1; 0.5-1: 1; 1-2: 1; 2-3: 1; 1-2.5: 1; or 1.5 to 2.0: 1, etc.
The molecular weight of the phenyl silicone rubber is 40-80 ten thousand. In some embodiments, the phenyl silicone rubber has a molecular weight of 40 to 50, 50 to 60, 60 to 70, or 70 to 80, etc. The content of phenyl in the phenyl silicone rubber is 5-40%. In some embodiments, the phenyl silicone rubber contains 5% to 10%, 10% to 20%, 20% to 30%, or 30% to 40% of phenyl groups.
When the methyl vinyl silicone rubber and the phenyl silicone rubber are used together, the mass ratio of the methyl vinyl silicone rubber to the phenyl silicone rubber is 0.1-10: 1. in some embodiments, the mass ratio of the methyl vinyl silicone rubber to the phenyl silicone rubber can be 0.1-1: 1, 1-2: 1, 2-3: 1, 3-4: 1, 4-5: 1, 5-6: 1, 6-7: 1, 7-8: 1, 8-9: 1, or 9-10: 1; or 0.1 to 5: 1; 5-10: 1, etc.
In the halogen-free flame-retardant heat-resistant silicone rubber composite material provided by the invention, the raw materials can also comprise 10-30% of white carbon black according to mass percentage. In some embodiments, the white carbon black may also be 10% to 15% by mass, 15% to 25% by mass; or 25% -30%, etc. The white carbon black is selected from fumed silica.
The halogen-free flame-retardant heat-resistant silicone rubber composite material provided by the invention can also comprise 10-50% of flame retardant by mass of the raw materials. In some embodiments, the mass percentage of the flame retardant may also be 20% -40%, 30% -50%; or 10% -20%, 20% -30%, 30% -40%, or 40% -50%. The flame retardant may be selected from one or more of modified aluminum hydroxide, aluminum hypophosphite, and combinations thereof, for example.
Wherein the modified aluminum hydroxide is silane modified aluminum hydroxide.
The halogen-free flame-retardant heat-resistant silicone rubber composite material provided by the invention can also comprise 5-40% of heat-resistant agent by mass percent of the raw materials. In some embodiments, the heat resistant agent may also be 10% to 30% by mass; 5% -20%, 20% -40%; or 5% -10%, 10% -20%, 20% -30%, or 30% -40%; or 10% -35%, 15% -30%, or 20% -25%. The heat-resistant agent is selected from calcined black iron oxide and/or nano titanium dioxide.
The halogen-free flame-retardant heat-resistant silicone rubber composite material provided by the invention can also comprise 1-10% of processing aid by mass percent of raw materials. In some embodiments, the mass percent of the processing aid can also be 1% -5%, 5% -10%; or 1% -3%, 3% -5%, 5% -8%, or 8% -10%; or 2% -9%, 3% -8%, 4% -7%, or 5% -6%. The processing aid is selected from one or more of hydroxyl silicone oil, a silane coupling agent and an antioxidant, wherein the mass ratio of the hydroxyl silicone oil to the silane coupling agent to the antioxidant is 10:1: 1.
The hydroxyl content in the hydroxyl silicone oil is 8-9%; 8% -8.5%; or 8.5% -9%, etc. Viscosity is 10-100 mpa.s; 10-50 mpa.s; 50-100 mpa.s; 10-30 mpa.s; 30-50 mpa.s; 50-80 mpa.s; or 80-100mpa.s, etc.
The silane coupling agent may be, for example, the silane coupling agent 172.
The antioxidant may be, for example, antioxidant 1010.
In one embodiment of the present invention, the substrate is,
the halogen-free flame-retardant heat-resistant silicone rubber composite material comprises the following raw materials in percentage by mass:
in a preferred embodiment of the present invention,
the halogen-free flame-retardant heat-resistant silicone rubber composite material comprises the following raw materials in percentage by mass:
the invention also provides a preparation method of the halogen-free flame-retardant heat-resistant silicone rubber composite material, which comprises the step of mixing and preparing silicone rubber, white carbon black, a flame retardant, a heat-resistant agent and a processing aid.
In the preparation method of the halogen-free flame-retardant heat-resistant silicone rubber composite material provided by the invention, the raw materials can be kneaded according to the proportion provided by the first aspect of the invention, and the kneading is carried out in a silicone rubber kneader. Adding the next material after the filler is added into the mixture and kneaded into a ball, finally heating to 120-140 ℃, vacuumizing for 0.5-1 hour, naturally cooling to below 25-30 ℃, and discharging the sheet by using an open mill.
The invention also provides application of the halogen-free flame-retardant heat-resistant silicone rubber composite material in the field of silicone rubber preparation.
The invention also provides silicon rubber which comprises the halogen-free flame-retardant heat-resistant silicon rubber composite material.
The preparation method of the silicone rubber comprises the steps of discharging the halogen-free flame-retardant heat-resistant silicone rubber composite material by an open mill, filtering, packaging and the like, so as to prepare the silicone rubber.
The high-performance halogen-free flame-retardant heat-resistant silicon rubber material prepared by the method has excellent physical and mechanical properties and excellent heat resistance, has a thermal decomposition temperature 50-100 ℃ higher than that of a common silicon rubber material, and can meet the application requirements of special industries such as military industry, high-speed rail and the like. The invention has simple process route and stable product quality, and is suitable for industrial production.
The following examples are provided to further illustrate the advantageous effects of the present invention.
In order to make the objects, technical solutions and advantageous technical effects of the present invention more clear, the present invention is further described in detail below with reference to examples. However, it should be understood that the embodiments of the present invention are only for explaining the present invention and are not for limiting the present invention, and the embodiments of the present invention are not limited to the embodiments given in the specification. The examples were prepared under conventional conditions or conditions recommended by the material suppliers without specifying specific experimental conditions or operating conditions.
Furthermore, it is to be understood that one or more method steps mentioned in the present invention does not exclude that other method steps may also be present before or after the combined steps or that other method steps may also be inserted between these explicitly mentioned steps, unless otherwise indicated; it is also to be understood that a combined connection between one or more devices/apparatus as referred to in the present application does not exclude that further devices/apparatus may be present before or after the combined device/apparatus or that further devices/apparatus may be interposed between two devices/apparatus explicitly referred to, unless otherwise indicated. Moreover, unless otherwise indicated, the numbering of the various method steps is merely a convenient tool for identifying the various method steps, and is not intended to limit the order in which the method steps are arranged or the scope of the invention in which the invention may be practiced, and changes or modifications in the relative relationship may be made without substantially changing the technical content.
In the following examples, reagents, materials and instruments used are commercially available unless otherwise specified.
Unless otherwise stated, the methyl vinyl silicone rubber manufacturer used was Toyue corporation, model number 110-8, with a vinyl content of 0.04%. The product of methyl vinyl silicone rubber with 0.16% vinyl content is the Dongye group, model 110-2.
The phenyl silicone rubber manufacturer is 108 model numbers of Guangzhou Laxol chemical technology Co.
The surface modified aluminum hydroxide is manufactured by American jaba and is OL-104 LEO.
The hydroxyl silicone oil manufacturer is Hubei Xinhaina, and the model is 300.
Example 1
500g of methyl vinyl silicone rubber with the vinyl content of 0.04 percent and the molecular weight of 80 ten thousand, 500g of methyl vinyl silicone rubber with the vinyl content of 1.6 percent and the molecular weight of 60 ten thousand, 300g of phenyl silicone rubber (with the phenyl content of 20 percent and the molecular weight of 60 ten thousand) are put into a 5L silicone rubber kneader, then 800g of fumed silica, 1300g of surface modified aluminum hydroxide, 500g of aluminum hypophosphite, 600g of calcined iron oxide black, 200g of nano titanium dioxide, 250g of processing aids such as hydroxyl silicone oil, 25 g of silane coupling agent 172, 25 g of antioxidant 1010 and the like are sequentially added in batches, the next material can be added after the fillers are added and kneaded into a mass each time, finally the temperature is raised to 120 ℃, the vacuum pumping is carried out for 1 hour, the materials are naturally cooled to the temperature below 50 ℃.
200g of the composite material is taken, 2.6g of bis-tetra-vulcanizing agent is added into an open mill and mixed uniformly, a sample piece with the thickness of 2mm is pressed at 140 ℃ for 10min, then secondary vulcanization is carried out for 4 hours at 200 ℃, and the sample piece is cut into standard sample pieces to be respectively tested for mechanical property, flame retardant property and TG. The performance test data are detailed in table 1.
Example 2
Adding 600g of methyl vinyl silicone rubber with the vinyl content of 0.04 percent and the molecular weight of 80 ten thousand, 600g of methyl vinyl silicone rubber with the vinyl content of 1.6 percent and the molecular weight of 60 ten thousand, 300g of phenyl silicone rubber (with the phenyl content of 20 percent and the molecular weight of 60 ten thousand) into a 5L silicone rubber kneader, then sequentially adding 900g of fumed silica, 1300g of surface modified aluminum hydroxide, 500g of aluminum hypophosphite, 600g of calcined iron oxide black, 200g of nano titanium dioxide, 250g of processing aids such as hydroxyl silicone oil, 25 g of silane coupling agent 172, 25 g of antioxidant 1010 and the like in batches, adding the next material after the filler is added into the mixture and kneaded into a mass, finally heating the mixture to 120 ℃, vacuumizing the mixture for 1 hour, naturally cooling the mixture to below 50 ℃, taking the mixture out of a pot, filtering and.
200g of the composite material is taken, 2.6g of bis-tetra-vulcanizing agent is added into an open mill and mixed uniformly, a sample piece with the thickness of 2mm is pressed at 140 ℃ for 10min, then secondary vulcanization is carried out for 4 hours at 200 ℃, and the sample piece is cut into standard sample pieces to be respectively tested for mechanical property, flame retardant property and TG. The performance test data are detailed in table 1.
Example 3
Adding 700g of methyl vinyl silicone rubber with the vinyl content of 0.04 percent and the molecular weight of 80 ten thousand, 700g of methyl vinyl silicone rubber with the vinyl content of 1.6 percent and the molecular weight of 60 ten thousand, 200g of phenyl silicone rubber (with the phenyl content of 20 percent and the molecular weight of 60 ten thousand) into a 5L silicone rubber kneader, then sequentially adding 1000g of fumed silica, 1000g of surface modified aluminum hydroxide, 600g of aluminum hypophosphite, 300g of calcined iron oxide black, 200g of nano titanium dioxide, 250g of processing aids such as hydroxyl silicone oil, 25 g of silane coupling agent 172, 25 g of antioxidant 1010 and the like in batches, adding the next material after the filler is added into the mixture and kneaded into a mass, finally heating the mixture to 120 ℃, vacuumizing the mixture for 1 hour, naturally cooling the mixture to below 50 ℃, taking the mixture out of a pot, filtering and.
200g of the composite material is taken, 2.6g of bis-tetra-vulcanizing agent is added into an open mill and mixed uniformly, a sample piece with the thickness of 2mm is pressed at 140 ℃ for 10min, then secondary vulcanization is carried out for 4 hours at 200 ℃, and the sample piece is cut into standard sample pieces to be respectively tested for mechanical property, flame retardant property and TG. The performance test data are detailed in table 1.
Example 4
Adding 800g of methyl vinyl silicone rubber with the vinyl content of 0.04 percent and the molecular weight of 80 ten thousand, 800g of methyl vinyl silicone rubber with the vinyl content of 1.6 percent and the molecular weight of 60 ten thousand and 200g of phenyl silicone rubber (with the phenyl content of 20 percent and the molecular weight of 60 ten thousand) into a 5L silicone rubber kneader, then sequentially adding 1200g of fumed silica, 1000g of aluminum hypophosphite, 400g of calcined iron oxide black, 300g of nano titanium dioxide, 250g of processing aids such as hydroxyl silicone oil, 25 g of silane coupling agent 172, 25 g of antioxidant 1010 and the like in batches, adding the next material after the filler is added each time and needs to be kneaded into a mass, finally heating to 120 ℃, vacuumizing for 1 hour, naturally cooling to below 50 ℃, taking out of a pot, filtering and packaging.
200g of the composite material is taken, 2.6g of bis-tetra-vulcanizing agent is added into an open mill and mixed uniformly, a sample piece with the thickness of 2mm is pressed at 140 ℃ for 10min, then secondary vulcanization is carried out for 4 hours at 200 ℃, and the sample piece is cut into standard sample pieces to be respectively tested for mechanical property, flame retardant property and TG. The performance test data are detailed in table 1.
Example 5
Adding 600g of methyl vinyl silicone rubber with the vinyl content of 0.04 percent and the molecular weight of 80 ten thousand into a 5L silicone rubber kneader, 600g of methyl vinyl silicone rubber with the vinyl content of 1.6 percent and the molecular weight of 60 ten thousand, 600g of phenyl silicone rubber (with the phenyl content of 20 percent and the molecular weight of 60 ten thousand), then sequentially adding 1100g of fumed silica, 200g of modified aluminum hydroxide, 1200g of aluminum hypophosphite, 300g of calcined iron oxide black, 100g of nano titanium dioxide, 250g of processing aids such as hydroxyl silicone oil, 25 g of silane coupling agent 172, 25 g of antioxidant 1010 and the like in batches, adding the next material after the filler is added into the mixture and kneaded into a mass, finally heating to 120 ℃, vacuumizing for 1 hour, naturally cooling to below 50 ℃, taking out of a pot, filtering and packaging.
200g of the composite material is taken, 2.6g of bis-tetra-vulcanizing agent is added into an open mill and mixed uniformly, a sample piece with the thickness of 2mm is pressed at 140 ℃ for 10min, then secondary vulcanization is carried out for 4 hours at 200 ℃, and the sample piece is cut into standard sample pieces to be respectively tested for mechanical property, flame retardant property and TG. The performance test data are detailed in table 1.
Example 6
Adding 500g of methyl vinyl silicone rubber with the vinyl content of 0.04 percent and the molecular weight of 80 ten thousand into a 5L silicone rubber kneader, 500g of methyl vinyl silicone rubber with the vinyl content of 1.6 percent and the molecular weight of 60 ten thousand, 1000g of phenyl silicone rubber (with the phenyl content of 20 percent and the molecular weight of 60 ten thousand), then sequentially adding 1000g of fumed silica, 300g of modified aluminum hydroxide, 1000g of aluminum hypophosphite, 300g of calcined iron oxide black, 100g of nano titanium dioxide, 250g of processing aids such as hydroxyl silicone oil, 25 g of silane coupling agent 172, 25 g of antioxidant 1010 and the like in batches, adding the next material after the filler is added into the mixture and kneaded into a mass, finally heating to 120 ℃, vacuumizing for 1 hour, naturally cooling to below 50 ℃, taking out of a pot, filtering and packaging.
200g of the composite material is taken, 2.6g of bis-tetra-vulcanizing agent is added into an open mill and mixed uniformly, a sample piece with the thickness of 2mm is pressed at 140 ℃ for 10min, then secondary vulcanization is carried out for 4 hours at 200 ℃, and the sample piece is cut into standard sample pieces to be respectively tested for mechanical property, flame retardant property and TG. The performance test data are detailed in table 1.
Comparative example 1
Adding 700g of methyl vinyl silicone rubber with the vinyl content of 0.04 percent and the molecular weight of 80 ten thousand into a 5L silicone rubber kneader, 700g of methyl vinyl silicone rubber with the vinyl content of 1.6 percent and the molecular weight of 60 ten thousand, then sequentially adding 1000g of fumed silica, 2000 g of modified aluminum hydroxide, 300g of aluminum hypophosphite, 250g of processing aids such as hydroxyl silicone oil, 25 g of silane coupling agent 172, 25 g of antioxidant 1010 and the like in batches, adding the next material after the filler is added and kneaded into a mass, finally heating to 120 ℃, vacuumizing for 1 hour, naturally cooling to below 50 ℃, taking out of the pot, filtering and packaging.
200g of the composite material is taken, 2.6g of bis-tetra-vulcanizing agent is added into an open mill and mixed uniformly, a sample piece with the thickness of 2mm is pressed at 140 ℃ for 10min, then secondary vulcanization is carried out for 4 hours at 200 ℃, and the sample piece is cut into standard sample pieces to be respectively tested for mechanical property, flame retardant property and TG. The performance test data are detailed in table 1.
Comparative example 2
Adding 800g of methyl vinyl silicone rubber with the vinyl content of 0.04 percent and the molecular weight of 80 ten thousand into a 5L silicone rubber kneader, 800g of methyl vinyl silicone rubber with the vinyl content of 1.6 percent and the molecular weight of 60 ten thousand, then sequentially adding 1000g of fumed silica, 1000g of modified aluminum hydroxide, 600g of aluminum hypophosphite, 300g of calcined iron oxide black, 200g of nano titanium dioxide, 250g of processing aids such as hydroxyl silicone oil, 25 g of silane coupling agent 172, 25 g of antioxidant 1010 and the like in batches, adding the next material after kneading into a mass after adding the filler each time, finally heating to 120 ℃, vacuumizing for 1 hour, naturally cooling to below 50 ℃, taking out of a pot, filtering and packaging.
200g of the composite material is taken, 2.6g of bis-tetra-vulcanizing agent is added into an open mill and mixed uniformly, a sample piece with the thickness of 2mm is pressed at 140 ℃ for 10min, then secondary vulcanization is carried out for 4 hours at 200 ℃, and the sample piece is cut into standard sample pieces to be respectively tested for mechanical property, flame retardant property and TG. The performance test data are detailed in table 1.
Comparative example 3
Adding 500g of methyl vinyl silicone rubber with the vinyl content of 0.04 percent and the molecular weight of 80 ten thousand into a 5L silicone rubber kneader, adding 500g of methyl vinyl silicone rubber with the vinyl content of 1.6 percent and the molecular weight of 60 ten thousand and 1000g of phenyl silicone rubber (with the phenyl content of 20 percent and the molecular weight of 60 ten thousand), then sequentially adding 1000g of fumed silica, 700g of modified aluminum hydroxide, 1000g of aluminum hypophosphite, 250g of processing aids such as hydroxyl silicone oil, 25 g of silane coupling agent 172, 25 g of antioxidant 1010 and the like in batches, adding the next material after kneading into a mass after adding the filler each time, finally heating to 120 ℃, vacuumizing for 1 hour, naturally cooling to below 50 ℃, taking out of a pot, filtering and packaging.
200g of the composite material is taken, 2.6g of bis-tetra-vulcanizing agent is added into an open mill and mixed uniformly, a sample piece with the thickness of 2mm is pressed at 140 ℃ for 10min, then secondary vulcanization is carried out for 4 hours at 200 ℃, and the sample piece is cut into standard sample pieces to be respectively tested for mechanical property, flame retardant property and TG. The performance test data are detailed in table 1.
The test results of the high-performance halogen-free flame-retardant heat-resistant silicone rubber prepared in each example and comparative example are shown in table 1:
| test items | Tensile strength | Elongation at break | Tear strength | Limiting oxygen index | UL94 flame retardance | Temperature of thermal decomposition |
| Unit of | MPa | ％ | kN/m | ％ | - | ℃ |
| Example 1 | 7 | 357 | 33 | 42 | V-0 | 463 |
| Example 2 | 7.5 | 385 | 35 | 41 | V-0 | 466 |
| Example 3 | 8.1 | 436 | 35 | 40 | V-0 | 468 |
| Example 4 | 8.8 | 455 | 36 | 39 | V-0 | 472 |
| Example 5 | 9.1 | 463 | 38 | 43 | V-0 | 475 |
| Example 6 | 9.5 | 460 | 37 | 45 | V-0 | 489 |
| Comparative example 1 | 7.1 | 330 | 18 | 40 | V-0 | 385 |
| Comparative example 2 | 7.8 | 391 | 20 | 42 | V-0 | 403 |
| Comparative example 3 | 9.6 | 480 | 38 | 46 | V-0 | 423 |
| Comparative example 4 | 11.5 | 750 | - | - | V-0 | 407 |
| Comparative example 5 | 10.9 | 629 | - | - | V-0 | 415 |
| Comparative example 6 | 10.2 | 707 | - | - | V-0 | 397 |
Comparative examples 4 to 6 the data are derived from patent CN 106633918. From the comparative data, the thermal decomposition temperature of the high-strength heat-resistant flame-retardant silicone rubber with the same mechanical property and flame-retardant grade is higher than that of the comparative example by more than 50 ℃, and the silicone rubber shows excellent heat resistance.
The test method comprises the following steps:
tensile strength test method:
determination of tensile stress strain property of vulcanized rubber or thermoplastic rubber by GB/T528-2009
Test method for elongation at break:
determination of tensile stress strain property of vulcanized rubber or thermoplastic rubber by GB/T528-2009
Tear strength test method:
determination of the tear Strength of vulcanized rubber or thermoplastic rubber Using GB/T529-2008 (trouser, Right Angle and crescent shaped samples)
The testing method of the limiting oxygen index comprises the following steps:
determination of the Combustion Performance of rubber by GB/T10707-2008
UL94 flame retardant test method:
vertical combustion with U.S. UL94
In conclusion, the present invention effectively overcomes various disadvantages of the prior art and has high industrial utilization value.
While the invention has been described with respect to a preferred embodiment, it will be understood by those skilled in the art that the foregoing and other changes, omissions and deviations in the form and detail thereof may be made without departing from the scope of this invention. Those skilled in the art can make various changes, modifications and equivalent arrangements, which are equivalent to the embodiments of the present invention, without departing from the spirit and scope of the present invention, and which may be made by utilizing the techniques disclosed above; meanwhile, any changes, modifications and variations of the above-described embodiments, which are equivalent to those of the technical spirit of the present invention, are within the scope of the technical solution of the present invention.
Claims (10)
1. The halogen-free flame-retardant heat-resistant silicone rubber composite material comprises the following raw materials in percentage by mass:
2. the halogen-free flame-retardant heat-resistant silicone rubber composite material according to claim 1, wherein the halogen-free flame-retardant heat-resistant silicone rubber composite material comprises the following raw materials in percentage by mass:
3. the halogen-free flame retardant heat resistant silicone rubber composite material according to claim 1 or 2, wherein the silicone rubber is selected from one or more of methyl vinyl silicone rubber, phenyl silicone rubber, and combinations thereof.
4. The halogen-free flame-retardant heat-resistant silicone rubber composite material according to claim 1 or 2, wherein the vinyl content in the methyl vinyl silicone rubber is 0.04% to 1.6%; the molecular weight of the methyl vinyl silicone rubber is 50-100 ten thousand.
5. The halogen-free flame-retardant heat-resistant silicone rubber composite material according to claim 1 or 2, wherein the methyl vinyl silicone rubber comprises a methyl vinyl silicone rubber having a vinyl content of 0.04% to 0.06% and a methyl vinyl silicone rubber having a vinyl content of 1.2% to 1.6%.
6. The halogen-free flame-retardant heat-resistant silicone rubber composite material according to claim 1 or 2, wherein the molecular weight of the phenyl silicone rubber is 40 to 80 ten thousand; the phenyl silicone rubber contains 5% -40% of phenyl.
7. The halogen-free flame-retardant heat-resistant silicone rubber composite material according to claim 1 or 2, characterized in that the white carbon black is selected from fumed silica;
and/or, the flame retardant is selected from one or more of surface modified aluminum hydroxide and aluminum hypophosphite;
and/or the heat-resistant agent is selected from calcined black iron oxide and/or nano titanium dioxide;
and/or the processing aid is selected from one or more of hydroxyl silicone oil, silane coupling agent and antioxidant.
8. The preparation method of the halogen-free flame-retardant heat-resistant silicone rubber composite material as claimed in claims 1 to 7, the preparation method comprising: the silicon rubber flame retardant is prepared by mixing silicon rubber, white carbon black, a flame retardant, a heat-resistant agent and a processing aid.
9. Use of the halogen-free flame-retardant heat-resistant silicone rubber composite material as defined in any one of claims 1 to 7 in the field of silicone rubber preparation.
10. A silicone rubber comprising the halogen-free flame retardant heat resistant silicone rubber composite material as claimed in any one of claims 1 to 7.
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| CN104761911A (en) * | 2015-04-03 | 2015-07-08 | 新安天玉有机硅有限公司 | High temperature mixing silicone rubber as well as preparation method and application thereof |
| CN104788965A (en) * | 2015-04-03 | 2015-07-22 | 新安天玉有机硅有限公司 | High-tear-resistance and corrosion-resistance silicone rubber as well as preparation method and application thereof |
| CN109867963A (en) * | 2019-01-14 | 2019-06-11 | 东莞市南炬高分子材料有限公司 | A kind of High-temperature-resandant andant flame-retardant silicone rubber and preparation method thereof |
| CN111004511A (en) * | 2019-12-30 | 2020-04-14 | 广东聚合科技股份有限公司 | High-strength high-temperature-resistant flame-retardant silicone rubber and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104761911A (en) * | 2015-04-03 | 2015-07-08 | 新安天玉有机硅有限公司 | High temperature mixing silicone rubber as well as preparation method and application thereof |
| CN104788965A (en) * | 2015-04-03 | 2015-07-22 | 新安天玉有机硅有限公司 | High-tear-resistance and corrosion-resistance silicone rubber as well as preparation method and application thereof |
| CN109867963A (en) * | 2019-01-14 | 2019-06-11 | 东莞市南炬高分子材料有限公司 | A kind of High-temperature-resandant andant flame-retardant silicone rubber and preparation method thereof |
| CN111004511A (en) * | 2019-12-30 | 2020-04-14 | 广东聚合科技股份有限公司 | High-strength high-temperature-resistant flame-retardant silicone rubber and preparation method thereof |
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