CN114836042A - High-temperature-resistant composite liquid silicone rubber - Google Patents
High-temperature-resistant composite liquid silicone rubber Download PDFInfo
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Abstract
The invention discloses high-temperature-resistant composite liquid silicone rubber which comprises the following raw materials in parts by weight: 80-120 parts of methyl vinyl silicone rubber, 15-30 parts of dimethyl cyclosiloxane, 12-22 parts of polymethylhydrosiloxane, 8-14 parts of cross-linking agent, 3-8 parts of inhibitor, 1-5 parts of high temperature resistant additive, 30-40 parts of filler, 4-7 parts of tackifier and 0.5-2 parts of catalyst. The high-temperature-resistant composite liquid silicone rubber has good mechanical properties, and also has good high-temperature resistance, flame retardance and electrical insulation.
Description
Technical Field
The invention relates to the technical field of rubber, in particular to high-temperature-resistant composite liquid silicone rubber.
Background
The silicon rubber is a rubber with a main chain formed by alternating silicon and oxygen atoms, and the silicon atoms are usually connected with two organic groups, and has application in the aspects of light industry, chemical industry, machinery, medicine and the like. The liquid silicone rubber is one of silicone rubbers, and is a silicone rubber organic elastomer which is formed by taking a polysiloxane organic polymer as a basic complex, adding a cross-linking agent, a reinforcing filler and other accessory ingredients, mixing and vulcanizing to form a linear structure as a main chain and is divided into condensed liquid silicone rubber and addition type liquid silicone rubber; the method is widely applied to the fields of energy power, industrial metallurgy, transportation and the like. Compared with solid silicone rubber, the liquid silicone rubber has excellent flowability, lower curing temperature and other processing properties, and is more flexible and faster.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides high-temperature-resistant composite liquid silicone rubber.
The technical scheme adopted by the invention is as follows:
the high-temperature-resistant composite liquid silicone rubber comprises the following raw materials in parts by weight: 80-120 parts of methyl vinyl silicone rubber, 15-30 parts of dimethyl cyclosiloxane, 12-22 parts of polymethylhydrosiloxane, 8-14 parts of cross-linking agent, 3-8 parts of inhibitor, 30-40 parts of filler, 4-7 parts of tackifier and 0.5-2 parts of catalyst.
Preferably, the high-temperature-resistant composite liquid silicone rubber comprises the following raw materials in parts by weight: 80-120 parts of methyl vinyl silicone rubber, 15-30 parts of dimethyl cyclosiloxane, 12-22 parts of polymethylhydrosiloxane, 8-14 parts of cross-linking agent, 3-8 parts of inhibitor, 1-5 parts of high temperature resistant additive, 30-40 parts of filler, 4-7 parts of tackifier and 0.5-2 parts of catalyst.
The preparation method of the high-temperature resistant additive comprises the following steps:
adding mica powder into 5-10 wt% nitric acid aqueous solution, and stirring at 50-60 ℃ for 1-3h, wherein the material-liquid ratio of the mica powder to the nitric acid aqueous solution is 1g (5-10) mL; filtering and drying to obtain pretreated mica powder; uniformly mixing pretreated mica powder, tetrabutyl titanate and 2-ethyl propyl acrylate, and carrying out ultrasonic treatment for 1-3h under the conditions of 20-30kHz and 350W of 200-; drying, calcining at 600-700 deg.C for 0.5-1h, cooling to room temperature, and micronizing to 5-10 μm to obtain modified mica powder; uniformly mixing nano tin oxide and modified mica powder, wherein the mass ratio of the nano tin oxide to the modified mica powder is 1 (3-5); then adding 1, 3-divinyl tetramethyl disilazane and tri (trimethylsiloxy) chlorosilane, and stirring for 5-10h at the temperature of 120-150 ℃, wherein the mass ratio of the 1, 3-divinyl tetramethyl disilazane, the tri (trimethylsiloxy) chlorosilane to the modified mica powder is 1 (1-2) to (15-20); obtaining the high-temperature resistant additive.
The cross-linking agent is one of tetraalkoxysilane, 2, 5-bis (tert-butylperoxy) -2, 5-dimethylhexane and methyltris (N-methylhexanamido) silane.
The inhibitor is one of 1-ethynyl-1-cyclohexanol and tetramethyl tetravinylcyclotetrasiloxane.
The tackifier is one or more than two of glycidoxypropyltrimethoxysilane, trimethylolpropane diallyl ether, allyl diglycol carbonate and hydroxyl vinyl siloxane.
The catalyst is one of chloroplatinic acid, stannous octoate and platinum catalyst.
The filler is one or more than two of aluminum hydroxide, zinc stannate, zinc borate, graphene, hexagonal boron nitride and functionalized boron nitride.
Preferably, the filler is functionalized boron nitride.
Hexagonal boron nitride (h-BN) is formed by the same number of B, N atoms arranged alternately and in sp 2 The new two-dimensional material formed by hybridization is similar to graphite structure and is called white graphite. The boron nitride nanosheet has excellent thermal stability, chemical corrosion resistance and oxidation resistance, and the unique two-dimensional lamellar structure of the boron nitride nanosheet can serve as a physical barrier in combustion to prevent heat conduction and diffusion of organic combustible molecules. However, boron nitride nanosheets, as flame retardants, have a tendency to stack up lamellae, have poor dispersibility in the matrix, and do not exhibit outstanding performance when used alone. Therefore, according to the invention, the boron nitride nanosheet is subjected to functional modification treatment, so that not only can the stacking of the lamella be inhibited, but also the flame retardance and the insulating property of the boron nitride nanosheet can be enhanced.
The ferric oxide is a traditional silicon rubber heat-resistant additive, on one hand, the rubber chains can be bonded to the surfaces of ferric oxide particles, the formation of volatile oligomers is prevented, and the stable crosslinking effect is added to the network; on the other hand, the compound can form a stable complex with the reaction center of siloxane molecules and is reductively coupled with iron ions through free radical elimination.
The preparation method of the functionalized boron nitride comprises the following steps:
s1, placing the hexagonal boron nitride into a muffle furnace to be calcined for 1-3h at the temperature of 900-1100 ℃ to obtain hydroxylated boron nitride;
s2, dispersing 4-8 parts by weight of the hydroxylated boron nitride obtained in the S1 in 500-700 parts by weight of isopropanol to obtain a dispersion liquid a; dissolving 5-7 parts by weight of ferric nitrate nonahydrate in 550 parts by weight of absolute ethyl alcohol to obtain solution b;
s3, adding the solution b prepared in the S2 into the dispersion liquid a, stirring at the room temperature at the rotation speed of 1000-1500rpm for 4-6h, adding 3-7 parts by weight of surfactant and 7-10 parts by weight of urea, continuing stirring for 1.5-3h, centrifuging, washing the obtained precipitate with deionized water, and drying at the temperature of 75-85 ℃ for 36-72h to obtain powder c; and placing the powder c in a muffle furnace, and calcining for 2-4h at the temperature of 450-550 ℃ to obtain the functionalized boron nitride.
Barium titanate has the advantages of large specific surface area, low dielectric loss, easy doping, good electrical insulation and the like, but the barium titanate nanoparticles are easy to aggregate, poor in dispersity in a matrix material and unobvious in service performance due to high surface energy of the barium titanate nanoparticles.
Further, the preparation method of the functionalized boron nitride comprises the following steps:
s1, placing the hexagonal boron nitride into a muffle furnace to be calcined for 1-3h at the temperature of 900-1100 ℃ to obtain hydroxylated boron nitride;
s2, dispersing 4-8 parts by weight of the hydroxylated boron nitride obtained in the S1 in 500-700 parts by weight of isopropanol to obtain a dispersion liquid a; dissolving 5-7 parts by weight of ferric nitrate nonahydrate in 550 parts by weight of absolute ethyl alcohol to obtain solution b;
s3, adding the solution b prepared in the S2 into the dispersion liquid a, stirring at the room temperature at the rotation speed of 1000-1500rpm for 4-6h, adding 3-7 parts by weight of surfactant and 7-10 parts by weight of urea, continuing stirring for 1.5-3h, centrifuging, washing the obtained precipitate with deionized water, and drying at the temperature of 75-85 ℃ for 36-72h to obtain powder c; placing the powder c in a muffle furnace, and calcining for 2-4h at the temperature of 450-550 ℃ to obtain modified boron nitride;
s4, adding 4-6 parts by weight of barium titanate into 30-45 parts by weight of deionized water, depolymerizing at the rotation speed of 1000rpm for 0.5-2h, adding 4-6 parts by weight of modified boron nitride obtained from S3, continuously stirring for 20-40min, adding 0.5-1.5 parts by weight of modifier, reacting at the temperature of 65-75 ℃ at 1000rpm for 4-6h, centrifuging, taking the precipitate, and drying at the temperature of 100 ℃ for 36-72h to obtain the functionalized boron nitride.
The surfactant is one of sodium dodecyl sulfate, sodium fatty alcohol ether sulfate, disodium sulfosuccinate monoester and fatty acid methyl ester sulfonate.
The modifier is 3-mercaptopropyltriethoxysilane or/and a silane coupling agent Si 747.
Preferably, the modifier is a mixture of 3-mercaptopropyltriethoxysilane and a silane coupling agent Si747, wherein the mass ratio of the 3-mercaptopropyltriethoxysilane to the silane coupling agent Si747 is 1 (2-4).
The invention successfully prepares the gamma-Fe by a sol-gel method 2 O 3 Loading the nano particles on a hydroxylated boron nitride nano sheet, then taking the obtained modified boron nitride nano sheet as a physical barrier to prevent the aggregation of the barium titanate nano particles, and finally grafting the modified boron nitride nano sheet and the barium titanate nano particle to the surfaces of the boron nitride nano sheet with hydroxyl groups and the barium titanate nano particle through condensation with a silane coupling agent to modify the boron nitride nano sheet and the barium titanate nano particle with hydroxyl groups, thereby obtaining the functionalized boron nitride.
According to the invention, the silane coupling agent is used as the modifier, on one hand, alkoxy in the coupling agent can react with hydroxyl on the surfaces of the boron nitride nano-sheets and the barium titanate nano-particles to form hydrogen bonds, so that the surface energy is reduced, and the compatibility with a base material is enhanced; on the other hand, the sulfydryl in the coupling agent can react with double bonds in the matrix-methyl vinyl silicone rubber and is connected with molecular chains, so that the dispersibility in the matrix material is improved, and the mechanical property of the material is improved.
A preparation method of high-temperature-resistant composite liquid silicone rubber comprises the following steps:
(1) weighing methyl vinyl silicone rubber, dimethyl cyclosiloxane, polymethylhydrosiloxane, inhibitor and cross-linking agent according to the weight parts, adding the materials into rubber mixing equipment, mixing for 15-25min at the temperature of 62-70 ℃, then adding filler, tackifier and catalyst, and mixing for 40-80min at the temperature of 25-35 ℃ to obtain a mixture;
(2) and (2) encapsulating the mixture obtained in the step (1) into a mold, standing at room temperature for curing for 10-20h, and discharging after curing is completed to obtain the high-temperature-resistant composite liquid silicone rubber.
Preferably, the preparation method of the high-temperature-resistant composite liquid silicone rubber comprises the following steps:
(1) weighing methyl vinyl silicone rubber, dimethyl cyclosiloxane, polymethylhydrosiloxane, inhibitor and cross-linking agent according to the weight parts, adding the materials into rubber mixing equipment, mixing for 15-25min at the temperature of 62-70 ℃, then adding high-temperature resistant additive, filler, tackifier and catalyst, and mixing for 40-80min at the temperature of 25-35 ℃ to obtain a mixture;
(2) and (2) encapsulating the mixture obtained in the step (1) into a mold, standing at room temperature for curing for 10-20h, and discharging after curing is completed to obtain the high-temperature-resistant composite liquid silicone rubber.
The invention has the beneficial effects that: the high-temperature-resistant composite liquid silicone rubber has good mechanical properties, and also has good high-temperature resistance, flame retardance and electrical insulation. According to the invention, barium titanate nano particles with high dielectric constant are compounded with boron nitride nano sheets by adopting a blending method, and are grafted and modified by using a coupling agent, so that the dispersibility of the flame-retardant filler in a matrix material can be further improved, and the introduction of the barium titanate nano particles also brings certain electrical insulation performance to the material. The preparation method is simple and easy to operate.
Detailed Description
The above summary of the present invention is described in further detail below with reference to specific embodiments, but it should not be understood that the scope of the above subject matter of the present invention is limited to the following examples.
Introduction of some raw materials in this application:
silane coupling agent Si747, also known as gamma-mercaptopropylethoxybis (propyl-hexaethoxy-siloxane), is available from Kjeldahl chemical Co., Ltd.
3-mercaptopropyltriethoxysilane, CAS No.: 14814-09-6, available from Nanjing Needend New Material technology, Inc.
2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane, CAS number: 78-63-7, available from Shanghai Michelin Biotechnology, Inc.
Polymethylhydrosiloxane, also known as hydrogen-containing silicone oil, CAS No.: 63148-57-2, available from Meivoler chemical Co., Ltd, Wuhan Ke.
Dimethyl cyclosiloxane, purity: 99.9%, refractive index (25 ℃): 1.3945, available from New gull chemical Co., Ltd, Hubei.
Glycidoxypropyltrimethoxysilane, CAS No.: 2530-83-8, and the content of effective substances: 99% of the total amount of the product obtained from ancient cooking vessel, Japan.
1-ethynyl-1-cyclohexanol, CAS number: 78-27-3, available from Shanghai Maxin Biotechnology, Inc.
Methyl vinyl silicone rubber, type: 110-2S, molecular weight: 62 ten thousand, vinyl content: 0.164% of silicone available from Nemontage Hengyu Hengji Co.
The platinum catalyst is a commercially available Kansted silicone oil type platinum catalyst and is available from Zhongxin organosilicon materials Co., Ltd.
Hexagonal boron nitride, particle size: 1 μm, purity: 99.9%, cargo number: NO-N-003-3, available from Shanghai Neio nanotechnology, Inc.
Disodium sulfosuccinate monoester, active content: 30% of the total amount of the compound, purchased from Australian chemical Co., Ltd.
Barium titanate, CAS No.: 12047-27-7, specification: 60nm, type: AM-BaTiO3-001-1, available from Yam nanotechnology, Inc., Zhejiang.
1, 3-divinyltetramethyldisilazane, CAS: 7691-02-3, available from McRael chemical technology, Inc., Shanghai.
Tris (trimethylsiloxy) chlorosilane, CAS: 17905-99-6, available from Chuqing New Material science and technology, Inc.
Mica powder, CAS: 12001-26-2, particle size 5 μm, available from Fosmann technologies, Inc. (Beijing).
Nano tin oxide, CAS: 18282-10-5, particle size of 200nm, and is available from Shanghai Bo micro applied materials technology Co.
Tetrabutyl titanate, CAS: 5593-70-4, from Hechengjing chemical Co., Ltd.
Ethyl 2-propylacrylate, CAS: 3550-06-9, available from Tianjin Xienci Biotechnology Ltd.
Example 1
The high-temperature-resistant composite liquid silicone rubber comprises the following raw materials in parts by weight: 100 parts of methyl vinyl silicone rubber, 20 parts of dimethyl cyclosiloxane, 15 parts of polymethylhydrosiloxane, 10 parts of 2, 5-bis (tert-butylperoxy) -2, 5-dimethylhexane, 5 parts of 1-ethynyl-1-cyclohexanol, 35 parts of hexagonal boron nitride, 5 parts of glycidoxypropyltrimethoxysilane and 1 part of platinum catalyst.
A preparation method of high-temperature-resistant composite liquid silicone rubber comprises the following steps:
(1) weighing methyl vinyl silicone rubber, dimethyl cyclosiloxane, polymethyl hydrogen siloxane, 1-ethynyl-1-cyclohexanol and 2, 5-bis (tert-butylperoxy) -2, 5-dimethyl hexane according to the weight parts, adding into rubber mixing equipment, mixing for 20min at 65 ℃, then adding hexagonal boron nitride, glycidoxypropyl trimethoxy silane and platinum catalyst, mixing for 60min at 30 ℃ to obtain a mixture;
(2) and (2) encapsulating the mixture obtained in the step (1) into a mold, standing at room temperature for curing for 12 hours, and discharging after curing is finished to obtain the high-temperature-resistant composite liquid silicone rubber.
Example 2
The high-temperature-resistant composite liquid silicone rubber comprises the following raw materials in parts by weight: 100 parts of methyl vinyl silicone rubber, 20 parts of dimethylcyclosiloxane, 15 parts of polymethylhydrosiloxane, 10 parts of 2, 5-bis (tert-butylperoxy) -2, 5-dimethylhexane, 5 parts of 1-ethynyl-1-cyclohexanol, 35 parts of functionalized boron nitride, 5 parts of glycidoxypropyltrimethoxysilane and 1 part of platinum catalyst.
The preparation method of the functionalized boron nitride comprises the following steps:
s1, putting the hexagonal boron nitride into a muffle furnace, and calcining for 2 hours at 1000 ℃ to obtain hydroxylated boron nitride;
s2, dispersing 5 parts by weight of the hydroxylated boron nitride obtained in S1 in 600 parts by weight of isopropanol to obtain a dispersion a; dissolving 6.5 parts by weight of ferric nitrate nonahydrate in 500 parts by weight of absolute ethyl alcohol to obtain a solution b;
s3, adding the solution b prepared in the S2 into the dispersion liquid a, stirring at the room temperature for 5 hours at the rotation speed of 1200rpm, adding 5 parts by weight of disodium sulfosuccinate and 8.5 parts by weight of urea, continuing stirring for 2 hours, centrifuging, washing the obtained precipitate with deionized water, and drying at the temperature of 80 ℃ for 48 hours to obtain powder c; and placing the powder c in a muffle furnace, and calcining for 3h at 500 ℃ to obtain the functionalized boron nitride.
A preparation method of high-temperature-resistant composite liquid silicone rubber comprises the following steps:
(1) weighing methyl vinyl silicone rubber, dimethyl cyclosiloxane, polymethyl hydrogen siloxane, 1-ethynyl-1-cyclohexanol and 2, 5-bis (tert-butylperoxy) -2, 5-dimethyl hexane according to the weight parts, adding into rubber mixing equipment, mixing for 20min at 65 ℃, then adding functional boron nitride, glycidoxypropyl trimethoxy silane and platinum catalyst, mixing for 60min at 30 ℃ to obtain a mixture;
(2) and (2) encapsulating the mixture obtained in the step (1) into a mold, standing at room temperature for curing for 12h, and discharging after curing to obtain the high-temperature-resistant composite liquid silicone rubber.
Example 3
The high-temperature-resistant composite liquid silicone rubber comprises the following raw materials in parts by weight: 100 parts of methyl vinyl silicone rubber, 20 parts of dimethyl cyclosiloxane, 15 parts of polymethylhydrosiloxane, 10 parts of 2, 5-bis (tert-butylperoxy) -2, 5-dimethylhexane, 5 parts of 1-ethynyl-1-cyclohexanol, 35 parts of functionalized boron nitride, 5 parts of glycidoxypropyltrimethoxysilane and 1 part of platinum catalyst.
The preparation method of the functionalized boron nitride comprises the following steps:
s1, putting the hexagonal boron nitride into a muffle furnace, and calcining for 2 hours at 1000 ℃ to obtain hydroxylated boron nitride;
s2, dispersing 5 parts by weight of the hydroxylated boron nitride obtained in the step S1 in 600 parts by weight of isopropyl alcohol to obtain a dispersion a; dissolving 6.5 parts by weight of ferric nitrate nonahydrate in 500 parts by weight of absolute ethyl alcohol to obtain a solution b;
s3, adding the solution b prepared in the S2 into the dispersion liquid a, stirring at the room temperature for 5 hours at the rotation speed of 1200rpm, adding 5 parts by weight of disodium sulfosuccinate and 8.5 parts by weight of urea, continuing stirring for 2 hours, centrifuging, washing the obtained precipitate with deionized water, and drying at the temperature of 80 ℃ for 48 hours to obtain powder c; placing the powder c in a muffle furnace, and calcining for 3 hours at 500 ℃ to obtain modified boron nitride;
s4, adding 5 parts by weight of barium titanate into 40 parts by weight of deionized water, depolymerizing for 1h at the rotating speed of 1000rpm, adding 5 parts by weight of modified boron nitride obtained from S3, continuing stirring for 30min, adding 0.8 part by weight of silane coupling agent Si747, reacting for 5h at 70 ℃ at 1000rpm, centrifuging, taking the precipitate, and drying for 48h at 100 ℃ to obtain the functionalized boron nitride.
A preparation method of high-temperature-resistant composite liquid silicone rubber comprises the following steps:
(1) weighing methyl vinyl silicone rubber, dimethyl cyclosiloxane, polymethyl hydrogen siloxane, 1-ethynyl-1-cyclohexanol and 2, 5-bis (tert-butylperoxy) -2, 5-dimethyl hexane according to the weight parts, adding into rubber mixing equipment, mixing for 20min at 65 ℃, then adding functional boron nitride, glycidoxypropyl trimethoxy silane and platinum catalyst, and mixing for 60min at 30 ℃ to obtain a mixture;
(2) and (2) encapsulating the mixture obtained in the step (1) into a mold, standing at room temperature for curing for 12h, and discharging after curing to obtain the high-temperature-resistant composite liquid silicone rubber.
Example 4
The high-temperature-resistant composite liquid silicone rubber comprises the following raw materials in parts by weight: 100 parts of methyl vinyl silicone rubber, 20 parts of dimethyl cyclosiloxane, 15 parts of polymethylhydrosiloxane, 10 parts of 2, 5-bis (tert-butylperoxy) -2, 5-dimethylhexane, 5 parts of 1-ethynyl-1-cyclohexanol, 35 parts of functionalized boron nitride, 5 parts of glycidoxypropyltrimethoxysilane and 1 part of platinum catalyst.
The preparation method of the functionalized boron nitride comprises the following steps:
s1, putting the hexagonal boron nitride into a muffle furnace, and calcining for 2 hours at 1000 ℃ to obtain hydroxylated boron nitride;
s2, dispersing 5 parts by weight of the hydroxylated boron nitride obtained in S1 in 600 parts by weight of isopropanol to obtain a dispersion a; dissolving 6.5 parts by weight of ferric nitrate nonahydrate in 500 parts by weight of absolute ethyl alcohol to obtain a solution b;
s3, adding the solution b prepared in the S2 into the dispersion liquid a, stirring at the room temperature for 5 hours at the rotation speed of 1200rpm, adding 5 parts by weight of disodium sulfosuccinate and 8.5 parts by weight of urea, continuing stirring for 2 hours, centrifuging, washing the obtained precipitate with deionized water, and drying at the temperature of 80 ℃ for 48 hours to obtain powder c; placing the powder c in a muffle furnace, and calcining for 3 hours at 500 ℃ to obtain modified boron nitride;
s4, adding 5 parts by weight of barium titanate into 40 parts by weight of deionized water, depolymerizing for 1 hour at the rotating speed of 1000rpm, adding 5 parts by weight of modified boron nitride obtained from S3, continuing stirring for 30 minutes, adding 0.8 part by weight of 3-mercaptopropyltriethoxysilane, reacting for 5 hours at 70 ℃ at 1000rpm, centrifuging, taking the precipitate, and drying for 48 hours at 100 ℃ to obtain the functionalized boron nitride.
A preparation method of high-temperature-resistant composite liquid silicone rubber comprises the following steps:
(1) weighing methyl vinyl silicone rubber, dimethyl cyclosiloxane, polymethyl hydrogen siloxane, 1-ethynyl-1-cyclohexanol and 2, 5-bis (tert-butylperoxy) -2, 5-dimethyl hexane according to the weight parts, adding into rubber mixing equipment, mixing for 20min at 65 ℃, then adding functional boron nitride, glycidoxypropyl trimethoxy silane and platinum catalyst, mixing for 60min at 30 ℃ to obtain a mixture;
(2) and (2) encapsulating the mixture obtained in the step (1) into a mold, standing at room temperature for curing for 12h, and discharging after curing to obtain the high-temperature-resistant composite liquid silicone rubber.
Example 5
The high-temperature-resistant composite liquid silicone rubber comprises the following raw materials in parts by weight: 100 parts of methyl vinyl silicone rubber, 20 parts of dimethyl cyclosiloxane, 15 parts of polymethylhydrosiloxane, 10 parts of 2, 5-bis (tert-butylperoxy) -2, 5-dimethylhexane, 5 parts of 1-ethynyl-1-cyclohexanol, 35 parts of functionalized boron nitride, 5 parts of glycidoxypropyltrimethoxysilane and 1 part of platinum catalyst.
The preparation method of the functionalized boron nitride comprises the following steps:
s1, putting the hexagonal boron nitride into a muffle furnace, and calcining for 2 hours at 1000 ℃ to obtain hydroxylated boron nitride;
s2, dispersing 5 parts by weight of the hydroxylated boron nitride obtained in S1 in 600 parts by weight of isopropanol to obtain a dispersion a; dissolving 6.5 parts by weight of ferric nitrate nonahydrate in 500 parts by weight of absolute ethyl alcohol to obtain a solution b;
s3, adding the solution b prepared in the S2 into the dispersion liquid a, stirring at the room temperature for 5 hours at the rotation speed of 1200rpm, adding 5 parts by weight of disodium sulfosuccinate and 8.5 parts by weight of urea, continuing stirring for 2 hours, centrifuging, washing the obtained precipitate with deionized water, and drying at the temperature of 80 ℃ for 48 hours to obtain powder c; placing the powder c in a muffle furnace, and calcining for 3 hours at 500 ℃ to obtain modified boron nitride;
s4, adding 5 parts by weight of barium titanate into 40 parts by weight of deionized water, depolymerizing for 1h at the rotating speed of 1000rpm, adding 5 parts by weight of modified boron nitride obtained from S3, continuing stirring for 30min, adding 0.8 part by weight of modifier, reacting for 5h at 70 ℃ at 1000rpm, centrifuging, taking the precipitate, and drying for 48h at 100 ℃ to obtain the functionalized boron nitride.
The modifier is a mixture of 3-mercaptopropyltriethoxysilane and a silane coupling agent Si747, wherein the mass ratio of the 3-mercaptopropyltriethoxysilane to the silane coupling agent Si747 is 1: 3.
A preparation method of high-temperature-resistant composite liquid silicone rubber comprises the following steps:
(1) weighing methyl vinyl silicone rubber, dimethyl cyclosiloxane, polymethyl hydrogen siloxane, 1-ethynyl-1-cyclohexanol and 2, 5-bis (tert-butylperoxy) -2, 5-dimethyl hexane according to the weight parts, adding into rubber mixing equipment, mixing for 20min at 65 ℃, then adding functional boron nitride, glycidoxypropyl trimethoxy silane and platinum catalyst, mixing for 60min at 30 ℃ to obtain a mixture;
(2) and (2) encapsulating the mixture obtained in the step (1) into a mold, standing at room temperature for curing for 12 hours, and discharging after curing is finished to obtain the high-temperature-resistant composite liquid silicone rubber.
Example 6
The high-temperature-resistant composite liquid silicone rubber comprises the following raw materials in parts by weight: 100 parts of methyl vinyl silicone rubber, 20 parts of dimethyl cyclosiloxane, 15 parts of polymethylhydrosiloxane, 10 parts of 2, 5-bis (tert-butylperoxy) -2, 5-dimethylhexane, 5 parts of 1-ethynyl-1-cyclohexanol, 3 parts of high temperature resistant additive, 35 parts of functionalized boron nitride, 5 parts of glycidoxypropyltrimethoxysilane and 1 part of platinum catalyst.
The preparation method of the high-temperature resistant additive comprises the following steps:
adding mica powder into 8 wt% nitric acid aqueous solution, and stirring at 55 ℃ for 1.5h, wherein the material-liquid ratio of the mica powder to the nitric acid aqueous solution is 1g:5 mL; filtering and drying to obtain pretreated mica powder; uniformly mixing pretreated mica powder, tetrabutyl titanate and 2-ethyl propyl acrylate, and carrying out ultrasonic treatment for 1h under the conditions of 25kHz and 300W, wherein the mass ratio of the pretreated mica powder to the tetrabutyl titanate to the 2-ethyl propyl acrylate is 10:3: 1; drying, calcining at 650 ℃ for 0.5h, cooling to room temperature, and micronizing to 5 μm to obtain modified mica powder; uniformly mixing nano tin oxide and modified mica powder, wherein the mass ratio of the nano tin oxide to the modified mica powder is 1: 4; then adding 1, 3-divinyl tetramethyl disilazane and tri (trimethylsiloxy) chlorosilane, and stirring at 130 ℃ for 8 hours, wherein the mass ratio of the 1, 3-divinyl tetramethyl disilazane to the tri (trimethylsiloxy) chlorosilane to the modified mica powder is 1:2: 17; obtaining the high-temperature resistant additive.
The preparation method of the functionalized boron nitride comprises the following steps:
s1, putting the hexagonal boron nitride into a muffle furnace, and calcining for 2 hours at 1000 ℃ to obtain hydroxylated boron nitride;
s2, dispersing 5 parts by weight of the hydroxylated boron nitride obtained in S1 in 600 parts by weight of isopropanol to obtain a dispersion a; dissolving 6.5 parts by weight of ferric nitrate nonahydrate in 500 parts by weight of absolute ethyl alcohol to obtain a solution b;
s3, adding the solution b prepared in the S2 into the dispersion liquid a, stirring at the room temperature for 5 hours at the rotation speed of 1200rpm, adding 5 parts by weight of disodium sulfosuccinate and 8.5 parts by weight of urea, continuing stirring for 2 hours, centrifuging, washing the obtained precipitate with deionized water, and drying at the temperature of 80 ℃ for 48 hours to obtain powder c; placing the powder c in a muffle furnace, and calcining for 3 hours at 500 ℃ to obtain modified boron nitride;
s4, adding 5 parts by weight of barium titanate into 40 parts by weight of deionized water, depolymerizing for 1h at the rotating speed of 1000rpm, adding 5 parts by weight of modified boron nitride obtained from S3, continuing stirring for 30min, adding 0.8 part by weight of modifier, reacting for 5h at 70 ℃ at 1000rpm, centrifuging, taking the precipitate, and drying for 48h at 100 ℃ to obtain the functionalized boron nitride.
The modifier is a mixture of 3-mercaptopropyltriethoxysilane and a silane coupling agent Si747, wherein the mass ratio of the 3-mercaptopropyltriethoxysilane to the silane coupling agent Si747 is 1: 3.
A preparation method of high-temperature-resistant composite liquid silicone rubber comprises the following steps:
(1) weighing methyl vinyl silicone rubber, dimethyl cyclosiloxane, polymethyl hydrogen siloxane, 1-ethynyl-1-cyclohexanol and 2, 5-bis (tert-butylperoxy) -2, 5-dimethyl hexane according to the weight parts, adding into rubber mixing equipment, mixing for 20min at 65 ℃, then adding a high temperature resistant additive, functionalized boron nitride, glycidoxypropyltrimethoxysilane and a platinum catalyst, and mixing for 60min at 30 ℃ to obtain a mixture;
(2) and (2) encapsulating the mixture obtained in the step (1) into a mold, standing at room temperature for curing for 12h, and discharging after curing to obtain the high-temperature-resistant composite liquid silicone rubber. The high temperature resistant composite liquid silicone rubber prepared in example 6 was subjected to an aging test at 500 ℃ for 72 hours, and the tensile strength thereof was measured to be 6.52MPa with reference to test example 1.
Comparative example 1
The high-temperature-resistant composite liquid silicone rubber comprises the following raw materials in parts by weight: 100 parts of methyl vinyl silicone rubber, 20 parts of dimethyl cyclosiloxane, 15 parts of polymethylhydrosiloxane, 10 parts of 2, 5-bis (tert-butylperoxy) -2, 5-dimethylhexane, 5 parts of 1-ethynyl-1-cyclohexanol, 3 parts of high temperature resistant additive, 35 parts of functionalized boron nitride, 5 parts of glycidoxypropyltrimethoxysilane and 1 part of platinum catalyst.
The preparation method of the high-temperature resistant additive comprises the following steps:
uniformly mixing nano tin oxide and mica powder, wherein the mass ratio of the nano tin oxide to the mica powder is 1: 4; then adding 1, 3-divinyl tetramethyl disilazane and tri (trimethylsiloxy) chlorosilane, and stirring at 130 ℃ for 8 hours, wherein the mass ratio of the 1, 3-divinyl tetramethyl disilazane to the tri (trimethylsiloxy) chlorosilane to the mica powder is 1:2: 17; obtaining the high-temperature resistant additive.
The preparation method of the functionalized boron nitride comprises the following steps:
s1, putting the hexagonal boron nitride into a muffle furnace, and calcining for 2 hours at 1000 ℃ to obtain hydroxylated boron nitride;
s2, dispersing 5 parts by weight of the hydroxylated boron nitride obtained in S1 in 600 parts by weight of isopropanol to obtain a dispersion a; dissolving 6.5 parts by weight of ferric nitrate nonahydrate in 500 parts by weight of absolute ethyl alcohol to obtain a solution b;
s3, adding the solution b prepared in the S2 into the dispersion liquid a, stirring at the room temperature for 5 hours at the rotation speed of 1200rpm, adding 5 parts by weight of disodium sulfosuccinate and 8.5 parts by weight of urea, continuing stirring for 2 hours, centrifuging, washing the obtained precipitate with deionized water, and drying at the temperature of 80 ℃ for 48 hours to obtain powder c; placing the powder c in a muffle furnace, and calcining for 3 hours at 500 ℃ to obtain modified boron nitride;
s4, adding 5 parts by weight of barium titanate into 40 parts by weight of deionized water, depolymerizing for 1h at the rotating speed of 1000rpm, adding 5 parts by weight of modified boron nitride obtained from S3, continuing stirring for 30min, adding 0.8 part by weight of modifier, reacting for 5h at 70 ℃ at 1000rpm, centrifuging, taking the precipitate, and drying for 48h at 100 ℃ to obtain the functionalized boron nitride.
The modifier is a mixture of 3-mercaptopropyltriethoxysilane and a silane coupling agent Si747, wherein the mass ratio of the 3-mercaptopropyltriethoxysilane to the silane coupling agent Si747 is 1: 3.
A preparation method of high-temperature-resistant composite liquid silicone rubber comprises the following steps:
(1) weighing methyl vinyl silicone rubber, dimethyl cyclosiloxane, polymethyl hydrogen siloxane, 1-ethynyl-1-cyclohexanol and 2, 5-bis (tert-butylperoxy) -2, 5-dimethyl hexane according to the weight parts, adding into rubber mixing equipment, mixing for 20min at 65 ℃, then adding a high temperature resistant additive, functionalized boron nitride, glycidoxypropyltrimethoxysilane and a platinum catalyst, and mixing for 60min at 30 ℃ to obtain a mixture;
(2) and (2) encapsulating the mixture obtained in the step (1) into a mold, standing at room temperature for curing for 12h, and discharging after curing to obtain the high-temperature-resistant composite liquid silicone rubber. After the high-temperature-resistant composite liquid silicone rubber prepared in comparative example 1 is subjected to a 72-hour aging test at 500 ℃, the tensile strength is determined to be 5.80MPa according to test example 1.
Test example 1
And (3) testing mechanical properties: the test was carried out according to GB/T528-2009 determination of tensile stress strain Properties of vulcanizates or thermoplastic rubbers. And testing by using an electronic universal testing machine, wherein the sample is dumbbell-shaped, the tensile speed is 500mm/min, the tensile strength and the elongation at break of the silicon rubber are recorded, 5 sample strips are formed on each group of samples, and the test is performed twice in parallel. The high temperature resistant composite liquid silicone rubbers prepared in examples 1 to 5 were tested.
TABLE 1 mechanical Property test results
| Tensile strength, MPa | Elongation at break, based on | |
| Example 1 | 3.43 | 385.6 |
| Example 2 | 4.52 | 448.7 |
| Example 3 | 6.91 | 561.3 |
| Example 4 | 6.59 | 549.8 |
| Example 5 | 7.85 | 605.4 |
The invention uses the functionalized boron nitride, obviously improves the dispersibility of the boron nitride as the filler in the matrix material; further, a silane coupling agent is used as a modifier for further modification, so that the mechanical property is greatly improved, and the reason is mainly as follows: on one hand, alkoxy in the coupling agent can react with hydroxyl on the surfaces of the boron nitride nanosheets and the barium titanate nanoparticles to form hydrogen bonds, so that the surface energy is reduced, and the compatibility with a base material is enhanced; on the other hand, the sulfydryl in the coupling agent can react with double bonds in the matrix-methyl vinyl silicone rubber and is connected with molecular chains, so that the dispersibility in the matrix material is improved, and the mechanical property of the material is improved.
Test example 2
And (3) testing the flame retardant property: the high temperature resistant composite liquid silicone rubbers prepared in examples 1 to 5 were respectively prepared into samples with a specification of 125X 10mm, and the limit oxygen index was tested according to GB/T10707-2008 "method for measuring the burning performance of rubber A-oxygen index method".
TABLE 2 flame retardancy test results
| LOI，％ | |
| Example 1 | 24.6 |
| Example 2 | 29.1 |
| Example 3 | 32.4 |
| Example 4 | 31.8 |
| Example 5 | 33.7 |
From the above results, it is understood that the flame retardant performance of example 2 is significantly better than that of example 1, probably due to γ -Fe 2 O 3 The quenching free radicals enhance the thermal stability of the matrix material, greatly improve the dispersibility of boron nitride in the matrix and promote the boron nitride to achieve the flame retardant effect through the barrier effect.
Test example 3
And (3) testing the insulating property: the volume resistivity of the high-temperature-resistant composite liquid silicone rubber prepared in the embodiments 1 to 5 of the invention is tested according to GB/T1692-2008 'determination of insulation resistivity of vulcanized rubber'.
TABLE 3 insulation Performance test results
| Volume resistivity, Ω/cm 3 | |
| Example 2 | 3.6×10 6 |
| Example 3 | 1.1×10 13 |
| Example 4 | 9.9×10 12 |
| Example 5 | 1.4×10 13 |
According to the invention, barium titanate nanoparticles with excellent electrical insulation performance are introduced into the functionalized boron nitride, so that the dispersibility and compatibility of the boron nitride in a matrix are improved, and a certain insulation performance is endowed to the material. Furthermore, 3-mercaptopropyltriethoxysilane and a silane coupling agent Si747 are compounded to serve as modifiers, synergy is achieved, the mechanical property of the material is improved, the steric hindrance is increased, the volume resistivity of the material is promoted to be improved, the insulating property of the material is further enhanced, and the application range of the material is expanded.
The foregoing detailed description of the preferred embodiments of the invention has been presented. It should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concepts. Therefore, the technical solutions available to those skilled in the art through logic analysis, reasoning and limited experiments based on the prior art according to the concept of the present invention should be within the scope of protection defined by the claims.
Claims (9)
1. The high-temperature-resistant composite liquid silicone rubber is characterized by comprising the following raw materials in parts by weight: 80-120 parts of methyl vinyl silicone rubber, 15-30 parts of dimethyl cyclosiloxane, 12-22 parts of polymethylhydrosiloxane, 8-14 parts of cross-linking agent, 3-8 parts of inhibitor, 1-5 parts of high temperature resistant additive, 30-40 parts of filler, 4-7 parts of tackifier and 0.5-2 parts of catalyst.
2. The high-temperature-resistant composite liquid silicone rubber according to claim 1, wherein the preparation method of the high-temperature-resistant additive comprises the following steps:
adding mica powder into 5-10 wt% nitric acid aqueous solution, and stirring at 50-60 ℃ for 1-3h, wherein the material-liquid ratio of the mica powder to the nitric acid aqueous solution is 1g (5-10) mL; filtering and drying to obtain pretreated mica powder; uniformly mixing pretreated mica powder, tetrabutyl titanate and 2-ethyl propyl acrylate, and carrying out ultrasonic treatment for 1-3h under the conditions of 20-30kHz and 350W of 200-; drying, calcining at 600-700 deg.C for 0.5-1h, cooling to room temperature, and micronizing to 5-10 μm to obtain modified mica powder; uniformly mixing nano tin oxide and modified mica powder, wherein the mass ratio of the nano tin oxide to the modified mica powder is 1 (3-5); then adding 1, 3-divinyl tetramethyl disilazane and tri (trimethylsiloxy) chlorosilane, and stirring for 5-10h at the temperature of 120-150 ℃, wherein the mass ratio of the 1, 3-divinyl tetramethyl disilazane, the tri (trimethylsiloxy) chlorosilane to the modified mica powder is 1 (1-2) to (15-20); obtaining the high-temperature resistant additive.
3. The high-temperature-resistant composite liquid silicone rubber according to claim 1, wherein the crosslinking agent is one of tetraalkoxysilane, 2, 5-bis (t-butylperoxy) -2, 5-dimethylhexane, and methyltris (N-methylhexanamido) silane.
4. The high temperature resistant composite liquid silicone rubber according to claim 1, wherein the inhibitor is one of 1-ethynyl-1-cyclohexanol and tetramethyltetravinylcyclotetrasiloxane.
5. The high-temperature-resistant composite liquid silicone rubber according to claim 1, wherein the tackifier is one or more than two of glycidoxypropyltrimethoxysilane, trimethylolpropane diallyl ether, allyl diglycol carbonate and hydroxyvinyl siloxane.
6. The high-temperature-resistant composite liquid silicone rubber according to claim 1, wherein the filler is one or more of aluminum hydroxide, zinc stannate, zinc borate, graphene, hexagonal boron nitride, and functionalized boron nitride.
7. The high-temperature-resistant composite liquid silicone rubber according to claim 6, wherein the functionalized boron nitride is prepared by the following method:
s1, placing the hexagonal boron nitride into a muffle furnace to be calcined for 1-3h at the temperature of 900-1100 ℃ to obtain hydroxylated boron nitride;
s2, dispersing 4-8 parts by weight of the hydroxylated boron nitride obtained in the S1 in 500-700 parts by weight of isopropanol to obtain a dispersion liquid a; dissolving 5-7 parts by weight of ferric nitrate nonahydrate in 550 parts by weight of absolute ethyl alcohol to obtain solution b;
s3, adding the solution b prepared in the S2 into the dispersion liquid a, stirring at the room temperature at the rotation speed of 1000-1500rpm for 4-6h, adding 3-7 parts by weight of surfactant and 7-10 parts by weight of urea, continuing stirring for 1.5-3h, centrifuging, washing the obtained precipitate with deionized water, and drying at the temperature of 75-85 ℃ for 36-72h to obtain powder c; placing the powder c in a muffle furnace, and calcining for 2-4h at the temperature of 450-550 ℃ to obtain modified boron nitride;
s4, adding 4-6 parts by weight of barium titanate into 30-45 parts by weight of deionized water, depolymerizing at the rotation speed of 1000rpm for 0.5-2h, adding 4-6 parts by weight of modified boron nitride obtained from S3, continuously stirring for 20-40min, adding 0.5-1.5 parts by weight of modifier, reacting at the temperature of 65-75 ℃ at 1000rpm for 4-6h, centrifuging, taking the precipitate, and drying at the temperature of 100 ℃ for 36-72h to obtain the functionalized boron nitride.
8. The high-temperature-resistant composite liquid silicone rubber according to claim 7, wherein the modifier is 3-mercaptopropyltriethoxysilane or/and a silane coupling agent Si 747.
9. The method for preparing the high-temperature-resistant composite liquid silicone rubber according to any one of claims 1 to 8, comprising the steps of:
(1) weighing methyl vinyl silicone rubber, dimethyl cyclosiloxane, polymethylhydrosiloxane, inhibitor and cross-linking agent according to the weight parts, adding the materials into rubber mixing equipment, mixing for 15-25min at the temperature of 62-70 ℃, then adding high-temperature resistant additive, filler, tackifier and catalyst, and mixing for 40-80min at the temperature of 25-35 ℃ to obtain a mixture;
(2) and (2) encapsulating the mixture obtained in the step (1) into a mold, standing at room temperature for curing for 10-20h, and discharging after curing is completed to obtain the high-temperature-resistant composite liquid silicone rubber.
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