CN112724544B - Heat-conducting vulcanized capsule and preparation method thereof - Google Patents
Heat-conducting vulcanized capsule and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
- C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
- C08L23/283—Halogenated homo- or copolymers of iso-olefins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
Abstract
The invention relates to the technical field of vulcanized capsules, in particular to a heat-conducting vulcanized capsule and a preparation method thereof, wherein the heat-conducting vulcanized capsule comprises the following steps: s100, according to rubber main materials: carbon black: heat-conducting filler: fiber filler: processing aid 100: (40-50): (10-20): (1-5): (3-6.5) mixing in a mass ratio to prepare a first-stage rubber compound; s200, adding a coordination aid and a vulcanization aid into the first-stage rubber compound in the S200, and mixing to prepare a second-stage rubber compound; s300, filtering and tabletting the two-stage rubber compound in the step S200, and curing; s400, injecting and vulcanizing the two-stage rubber compound cured in the step S300; and S400, obtaining the heat-conducting curing bladder. The heat-conducting vulcanized capsule provided by the invention has the advantages of high heat conductivity, good mechanical property, high vulcanization speed and good comprehensive use performance.
Description
Technical Field
The invention relates to the technical field of vulcanized capsules, in particular to a heat-conducting vulcanized capsule and a preparation method thereof.
Background
The vulcanizing capsule is a hollow thin-wall rubber product of a tire vulcanizing machine, is filled into an inner cavity of a tire blank to be vulcanized, is filled with a heating medium, and is matched with the vulcanizing machine for shaping and vulcanizing.
And putting the molded tire blank on a vulcanizing machine, vulcanizing at a certain temperature, time and pressure, wherein the vulcanization is to transfer heat to the tire blank from the inner side and the outer side of the tire blank, the tire blank absorbs heat, cross-linking is generated among molecular chains, and the tire blank becomes an elastomer after the cross-linking reaches a certain degree, namely the tire. The outer side of the tire blank is subjected to heat transfer by a tire steel die, and the inner side of the tire blank is subjected to heat transfer by a tire vulcanization capsule. The heat conduction of the steel die is fast, and the heat conduction of the vulcanization capsule is slow because the vulcanization capsule is made of rubber products, so that the outer side vulcanization of the tire is fast, the inner side vulcanization is slow, the vulcanization speed is not uniform, and the quality of the final tire product is influenced. Therefore, the heat conductivity of the vulcanization capsule is improved, the vulcanization quality of the tire can be ensured, the vulcanization speed can be improved, the vulcanization time is shortened, the energy is saved, and the labor productivity is improved.
In the production and processing process of the vulcanized capsule, the vulcanization process is a process that the physicochemical properties of rubber are changed, and the unvulcanized rubber is changed into vulcanized rubber through a series of complex chemical crosslinking processes, so that a plastic substance is changed into an elastic substance, and the vulcanized capsule has good physical and mechanical properties and chemical properties.
Disclosure of Invention
In order to solve at least one of the above technical problems,
the invention provides a preparation method of a heat-conducting curing capsule, which comprises the following steps:
s100, according to rubber main materials: carbon black: heat-conducting filler: fiber filler: processing aid = 100: (40-50): (10-20): (1-5): (3-6.5) mixing in a mass ratio to prepare a first-stage rubber compound;
s200, adding a coordination aid and a vulcanization aid into the first-stage rubber compound in the step S100, and mixing to prepare a second-stage rubber compound;
s300, filtering and tabletting the two-stage rubber compound in the step S200, and curing;
s400, injecting and vulcanizing the two-stage rubber compound cured in the step S300;
s500, obtaining the heat-conducting curing capsule;
the coordination aid in the step S200 is at least one of zinc stearate and zinc acrylate;
the vulcanization aid in the step S200 comprises stearic acid, zinc oxide and phenolic resin; the adjacent hydroxymethyl content of the phenolic resin is more than 6 percent.
The heat-conducting filler can greatly improve the heat-conducting property of the curing bladder, but the elastic property of the curing bladder is often influenced along with the increase of the using amount of the heat-conducting filler, such as the reduction of tearing strength, elongation at break and the like. In order to compensate the performance loss, the fiber filler is added into the rubber main material, and the fiber filler can greatly improve the tearing strength of the vulcanized capsule and improve the comprehensive performance of the vulcanized capsule. The phenolic resin with the critical hydroxymethyl content of more than 6 percent is used as the vulcanizing agent, because the critical hydroxymethyl content of the phenolic resin has great influence on the vulcanizing performance of the phenolic resin, when the hydroxymethyl content is less than 1 percent, the phenolic resin lacks the crosslinking capability and can not be vulcanized, and the rubber compound is always in an unvulcanized state. When the content of the hydroxymethyl group is more than 6%, the normal crosslinking capability can be realized.
Preferably, the mass ratio of the rubber main material in the step S100 to the stearic acid, the zinc oxide and the phenolic resin in the coordination aid and the vulcanization aid in the step S200 is as follows: coordination aid: stearic acid: zinc oxide: phenolic resin = 100: (1-5): (0.2-0.5): (5-10): (2-4); the mixing temperature in the step S100 is 130-150 ℃, and the mixing temperature in the step S200 is 160-180 ℃.
Preferably, the rubber main material in step S100 includes butyl rubber with low unsaturation degree and modified brominated butyl rubber, and the modified brominated butyl rubber is obtained by grafting demethylated lignin to brominated butyl rubber.
Butyl rubber is one of synthetic rubbers, has good chemical and thermal stability, and has outstanding air and water tightness advantages. However, the unsaturated double bond in the butyl rubber affects the mechanical stability of the vulcanized capsule under high temperature conditions, so that the vulcanized capsule is easy to age. Therefore, the butyl rubber with low unsaturation degree is adopted in the production formula, the content of double bonds is reduced, the thermal stability of the vulcanized capsule is effectively improved, and the aging resistance of the vulcanized capsule is improved.
When butyl rubber is used alone, the vulcanization rate is low and the dispersibility of a filler such as carbon black in butyl rubber is poor. The vulcanization speed can be effectively improved by using the modified brominated butyl rubber and the butyl rubber together. The demethylated lignin contains a large amount of polar groups, and the polarity of a rubber chain segment can be improved after the demethylated lignin is subjected to grafting reaction with bromobutyl rubber, so that the dispersibility of carbon black and other fillers in a rubber matrix is improved.
Preferably, the heat-conducting filler is a boron-nitrogen polymer modified by nano silver, and the boron-nitrogen polymer is one or more of hexagonal boron nitride, cubic boron nitride and rhombohedral boron nitride.
The boron-nitrogen polymer has excellent heat conductivity, after the boron-nitrogen polymer is modified by nano silver, silver ions are attached to the surface of the boron-nitrogen polymer, and effective heat conduction paths are formed among the boron-nitrogen polymers through the silver ions attached to the surface of the boron-nitrogen polymer, so that the thermal contact resistance among the boron-nitrogen polymers is reduced, and the heat conductivity of the vulcanized capsule is greatly improved.
Preferably, the carbon black in the step S100 includes acetylene black.
The acetylene black has good thermal conductivity, and can further improve the thermal conductivity of the curing bladder.
Preferably, the fibrous filler in step S100 is aramid staple fiber treated with dopamine.
The aramid short fiber is a flexible fiber, can be used at a high temperature of 220 ℃ for a long time without aging, and has lasting thermal stability. Meanwhile, the aramid short fiber also has excellent wear-resistant and tear-resistant properties, and can effectively improve the comprehensive properties of the vulcanized capsule. The aramid short fiber treated by the dopamine solution can improve the surface property of the aramid short fiber and improve the dispersibility of the aramid short fiber in a rubber main body.
Preferably, the processing aid in step S100 includes castor oil and microcrystalline wax.
The castor oil has low molecular weight, can improve the fluidity of rubber materials and the processing performance of a rubber main body, and the microcrystalline wax can increase the bonding degree in the vulcanization process and reduce the generation of secondary and waste products such as heavy skin, bubbles and the like.
Preferably, the step S100 specifically includes:
step S110, mixing phenol, lignin and a hydrogen bromide solution, reacting for 1-4 hours in microwaves at 80-120 ℃, adding water for dilution after the reaction is finished, adjusting the pH value to be =2, and centrifuging, washing and drying to obtain demethylated lignin;
s120, mixing the demethylated lignin obtained in the step S110 with bromobutyl rubber at 70-110 ℃ for 5-20 minutes to obtain modified bromobutyl rubber;
s130, adding butyl rubber into the modified brominated butyl rubber in the step S120, and banburying at 130-150 ℃ to obtain the rubber main material;
s140, uniformly mixing acetylene carbon black and carbon black N330 at room temperature to obtain the carbon black;
s150, adding the boron-nitrogen polymer into a sodium hydroxide solution, stirring for 40-48 hours at 100-120 ℃, and cleaning and drying to obtain a primary treatment boron-nitrogen polymer;
s160, adding a silane coupling agent into an ethanol solution, stirring for 30-50 minutes at 50-60 ℃ to obtain a mixed solution, adding the primary treatment boron-nitrogen polymer obtained in the step S150 into the mixed solution, stirring for 18-24 hours at 100-120 ℃, filtering, and drying to obtain a secondary treatment boron-nitrogen polymer;
s170, mixing the secondary-treatment boron-nitrogen polymer obtained in the step S160 with dimethylformamide, uniformly stirring, adding a silver nitrate solution, mixing and stirring at 60-80 ℃ for 1-2 hours, standing at room temperature for 18-24 hours, washing and drying to obtain the heat-conducting filler;
step S180, cutting aramid fibers into aramid staple fibers with the length of 2-5 mm, soaking the aramid staple fibers in a dopamine solution, preserving heat at 65 ℃ for 4 hours, adding a silane coupling agent, uniformly stirring, continuously preserving heat at 65 ℃ for 4 hours, taking out the aramid staple fibers, washing with water, and drying to obtain the fiber filler;
step S190, adding the carbon black obtained in the step S140, the heat-conducting filler obtained in the step S170, the fiber filler obtained in the step S180 and the processing aid obtained in the step S100 into the rubber main material obtained in the step S130, and mixing at 130-150 ℃ to prepare the rubber compound.
Preferably, in step S110, the mass fraction of the hydrogen bromide solution is 45%, and the mass ratio of the phenol to the lignin to the hydrogen bromide solution is phenol: lignin: hydrogen bromide solution = 100: (10-50): (2-10); and/or
In the step S120, the mass ratio of the bromobutyl rubber to the demethylated lignin is bromobutyl rubber: demethylated lignin = 100: (1-40); and/or
In the step S130, the mass ratio of the butyl rubber to the modified brominated butyl rubber is butyl rubber: modified brominated butyl rubber = (50-90): (10-50); and/or
In the step S140, the mass ratio of the acetylene black to the carbon black N330 is acetylene black: carbon black N330=2: 1; and/or
In the step S150, the mass fraction of sodium hydroxide in the sodium hydroxide solution is 20%, and the mass ratio of the sodium hydroxide solution to the boron nitride polymer is: boron nitrogen macromolecule = 100: (2-5); and/or
In the step S160, the mass fraction of ethanol in the ethanol solution is greater than 95%, and the mass ratio of the ethanol solution to the silane coupling agent is: silane coupling agent = 100: (0.05-0.15); the mass ratio of the mixed solution to the boron-nitrogen polymer subjected to primary treatment is mixed solution: primary treatment of boron nitrogen polymer = 100: (5-10); and/or
In the step S170, the mass fraction of silver nitrate in the silver nitrate solution is 0.15%, and the mass ratio of the dimethylformamide, the secondarily processed boron-nitrogen polymer, and the silver nitrate solution is dimethylformamide: secondary treatment of boron-nitrogen polymer: silver nitrate solution = 100: (1-5): (2-7); and/or
In the step S180, the dopamine accounts for 2% by mass of the dopamine solution, and the silane coupling agent accounts for 2% by mass of the dopamine solution; and/or
In the step S190, the mass ratio of the castor oil to the microcrystalline wax in the processing aid is castor oil: microcrystalline wax = (2-5): (1-1.5).
A heat-conducting vulcanized capsule is prepared by the preparation method of the heat-conducting vulcanized capsule.
Compared with the prior art, the invention has the following beneficial technical effects:
1. the heat-conducting filler and the fiber filler are matched with each other to obtain the vulcanized capsule with heat-conducting property and mechanical property;
2. the butyl rubber and the brominated butyl rubber modified by the demethylated lignin are compounded for use, so that the dispersibility of carbon black and other fillers in the main rubber material is improved, and the vulcanized capsule with good quality uniformity and high comprehensive mechanical property is obtained; in addition, the addition of the brominated butyl rubber also improves the vulcanization activity and reduces the vulcanization time;
3. the boron-nitrogen macromolecules modified by nano silver are used as heat conducting fillers, and effective heat conducting paths are formed among the boron-nitrogen macromolecules through silver ions attached to the surfaces of the boron-nitrogen macromolecules, so that the thermal contact resistance among the boron-nitrogen macromolecules is reduced, and the heat conductivity of the curing capsule is improved;
4. the dispersion of the aramid short fiber in the rubber main material and the tearing strength of the vulcanized capsule are improved by adopting the aramid short fiber modified by the dopamine solution;
in conclusion, the heat-conducting vulcanized capsule provided by the invention has the advantages of high heat conductivity, good mechanical property, high vulcanization speed and good comprehensive use performance.
Detailed Description
The embodiment of the invention provides a preparation method of a heat-conducting curing capsule, which comprises the following steps:
s100, according to rubber main materials: carbon black: heat-conducting filler: fiber filler: processing aid = 100: (40-50): (10-20): (1-5): (3-6.5) mixing in a mass ratio to prepare a first-stage rubber compound;
s200, adding a coordination aid and a vulcanization aid into the first-stage rubber compound in the step S100, and mixing to prepare a second-stage rubber compound;
s300, filtering and tabletting the two-stage rubber compound in the step S200, and curing;
s400, injecting and vulcanizing the two-stage rubber compound cured in the step S300;
s500, obtaining the heat-conducting curing bladder;
the coordination aid in the step S200 is at least one of zinc stearate and zinc acrylate;
the vulcanization aid in the step S200 comprises stearic acid, zinc oxide and phenolic resin; the adjacent hydroxymethyl content of the phenolic resin is more than 6 percent.
In this embodiment, the heat conductive filler can greatly improve the heat conductive performance of the curing bladder, but with the increase of the usage amount of the heat conductive filler, the elastic performance of the curing bladder is often affected, for example, the tearing strength and the elongation at break are reduced. In order to compensate the performance loss, the fiber filler is added in the embodiment, and the fiber filler can greatly improve the tearing strength of the curing bladder and improve the comprehensive performance of the curing bladder. The phenolic resin with the critical hydroxymethyl content of more than 6 percent is used as the vulcanizing agent, because the critical hydroxymethyl content of the phenolic resin has great influence on the vulcanizing performance of the phenolic resin, when the hydroxymethyl content is less than 1 percent, the phenolic resin lacks the crosslinking capability and can not be vulcanized, and the rubber compound is always in an unvulcanized state. And when the content of the hydroxymethyl group is more than 6 percent, the normal crosslinking capacity can be realized.
In some embodiments of the present invention, the mass ratio of the rubber main material in the step S100 to the stearic acid, the zinc oxide, and the phenolic resin in the coordination aid and the vulcanization aid in the step S200 is rubber main material: coordination aid: stearic acid: zinc oxide: phenolic resin = 100: (1-5): (0.2-0.5): (5-10): (2-4); the mixing temperature in the step S100 is 130-150 ℃, and the mixing temperature in the step S200 is 160-180 ℃.
In some embodiments of the present invention, the rubber main material in step S100 includes a butyl rubber with low unsaturation degree and a modified brominated butyl rubber, and the modified brominated butyl rubber is obtained by grafting a demethylated lignin to a brominated butyl rubber.
Butyl rubber is one of synthetic rubbers, has good chemical and thermal stability, and has outstanding air and water tightness advantages. However, the unsaturated double bond in the butyl rubber affects the mechanical stability of the vulcanized capsule at high temperature, so that the vulcanized capsule is easy to age. Therefore, the butyl rubber with low unsaturation degree is adopted in the production formula, the content of double bonds is reduced, the thermal stability of the vulcanized capsule is effectively improved, and the aging resistance of the vulcanized capsule is improved.
When butyl rubber is used alone, the vulcanization rate is low and the dispersibility of a filler such as carbon black in butyl rubber is poor. The vulcanization speed can be effectively improved by using the modified brominated butyl rubber and the butyl rubber together. The demethylated lignin contains a large amount of polar groups, and the polarity of a rubber chain segment can be improved after the demethylated lignin is subjected to grafting reaction with bromobutyl rubber, so that the dispersibility of carbon black and other fillers in a rubber matrix is improved.
In some embodiments of the present invention, the heat conductive filler is a boron-nitrogen polymer modified by nano silver, and the boron-nitrogen polymer is one or more of hexagonal boron nitride, cubic boron nitride, and rhombohedral boron nitride.
The boron-nitrogen polymer has excellent heat conductivity, after the modification of the nano silver, silver ions are attached to the surface of the boron-nitrogen polymer, and effective heat conduction paths are formed among the boron-nitrogen polymers through the silver ions attached to the surface of the boron-nitrogen polymer, so that the thermal contact resistance among the boron-nitrogen polymers is reduced, and the heat conductivity of the vulcanization capsule is greatly improved.
In some embodiments of the invention, the carbon black of step S100 comprises acetylene black.
The acetylene black has good thermal conductivity, and can further improve the thermal conductivity of the vulcanization capsule.
In some embodiments of the present invention, the fibrous filler in step S100 is a dopamine-treated aramid staple fiber.
The aramid short fiber is a flexible fiber, can be used at a high temperature of 220 ℃ for a long time without aging, and has lasting thermal stability. Meanwhile, the aramid short fiber also has excellent wear-resistant and tear-resistant properties, and can effectively improve the comprehensive properties of the vulcanized capsule. The aramid short fiber treated by the dopamine solution can improve the surface performance of the aramid short fiber and improve the dispersibility of the aramid short fiber in the rubber main material.
In some embodiments of the present invention, the processing aid in step S100 comprises castor oil and microcrystalline wax.
The castor oil has low molecular weight, can improve the fluidity of rubber materials and the processability of rubber main materials, and the microcrystalline wax can increase the bonding degree in the vulcanization process and reduce secondary and waste products such as heavy skin, bubbles and the like.
In some embodiments of the present invention, the step S100 specifically includes:
step S110, mixing phenol, lignin and a hydrogen bromide solution, reacting for 1-4 hours in a microwave at 80-120 ℃, adding water for dilution after the reaction is finished, adjusting the pH value to be =2, centrifuging, washing and drying to obtain demethylated lignin;
s120, mixing the demethylated lignin obtained in the step S110 with bromobutyl rubber at 70-110 ℃ for 5-20 minutes to obtain modified bromobutyl rubber;
s130, adding butyl rubber into the modified brominated butyl rubber in the step S120, and banburying at 130-150 ℃ to obtain the rubber main material;
s140, uniformly mixing acetylene carbon black and carbon black N330 at room temperature to obtain the carbon black;
s150, adding the boron-nitrogen polymer into a sodium hydroxide solution, stirring for 40-48 hours at 100-120 ℃, and cleaning and drying to obtain a primary treatment boron-nitrogen polymer;
s160, adding a silane coupling agent into an ethanol solution, stirring for 30-50 minutes at 50-60 ℃ to obtain a mixed solution, adding the primary treatment boron-nitrogen polymer obtained in the step S150 into the mixed solution, stirring for 18-24 hours at 100-120 ℃, filtering, and drying to obtain a secondary treatment boron-nitrogen polymer;
s170, mixing the secondary-treatment boron-nitrogen polymer obtained in the step S160 with dimethylformamide, uniformly stirring, adding a silver nitrate solution, mixing and stirring at 60-80 ℃ for 1-2 hours, standing at room temperature for 18-24 hours, washing and drying to obtain the heat-conducting filler;
step S180, cutting aramid fibers into aramid staple fibers with the length of 2-5 mm, soaking the aramid staple fibers in a dopamine solution, preserving heat at 65 ℃ for 4 hours, adding a silane coupling agent, uniformly stirring, continuously preserving heat at 65 ℃ for 4 hours, taking out the aramid staple fibers, washing with water, and drying to obtain the fiber filler;
step S190, adding the carbon black obtained in the step S140, the heat-conducting filler obtained in the step S170, the fiber filler obtained in the step S180 and the processing aid obtained in the step S100 into the rubber main material obtained in the step S130, and mixing at 130-150 ℃ to prepare the rubber compound.
In some embodiments of the present invention, in step S110, the mass fraction of the hydrogen bromide solution is 45%, and the mass ratio of the phenol, the lignin, and the hydrogen bromide solution is phenol: lignin: hydrogen bromide solution = 100: (10-50): (2-10); and/or
In the step S120, the mass ratio of the bromobutyl rubber to the demethylated lignin is bromobutyl rubber: demethylated lignin = 100: (1-40); and/or
In the step S130, the mass ratio of the butyl rubber to the modified brominated butyl rubber is butyl rubber: modified brominated butyl rubber = (50-90): (10-50); and/or
In the step S140, the mass ratio of the acetylene black to the carbon black N330 is acetylene black: carbon black N330=2: 1; and/or
In the step S150, the mass fraction of sodium hydroxide in the sodium hydroxide solution is 20%, and the mass ratio of the sodium hydroxide solution to the boron nitride polymer is: boron nitrogen macromolecule = 100: (2-5); and/or
In the step S160, the mass fraction of ethanol in the ethanol solution is greater than 95%, and the mass ratio of the ethanol solution to the silane coupling agent is: silane coupling agent = 100: (0.05-0.15); the mass ratio of the mixed solution to the boron-nitrogen polymer subjected to primary treatment is mixed solution: primary treatment of boron nitrogen polymer = 100: (5-10); and/or
In the step S170, the mass fraction of silver nitrate in the silver nitrate solution is 0.15%, and the mass ratio of the dimethylformamide, the secondarily processed boron-nitrogen polymer, and the silver nitrate solution is dimethylformamide: secondary treatment of boron-nitrogen polymer: silver nitrate solution = 100: (1-5): (2-7); and/or
In the step S180, the dopamine accounts for 2% by mass of the dopamine solution, and the silane coupling agent accounts for 2% by mass of the dopamine solution; and/or
In the step S190, the mass ratio of the castor oil to the microcrystalline wax in the processing aid is castor oil: microcrystalline wax = (2-5): (1-1.5).
Example 1
The embodiment provides a preparation method of a heat-conducting curing capsule, which comprises the following steps:
step S1. add phenol: lignin: hydrogen bromide solution = 100: 10: 2, mixing phenol, lignin and a hydrogen bromide solution with the mass fraction of 45%, reacting for 1-4 hours in a microwave at the temperature of 80-120 ℃, adding water for dilution after the reaction is finished, adjusting the pH value to be =2, centrifuging, washing and drying to obtain demethylated lignin;
step S2, the demethylated lignin obtained in the step S1 is processed according to the proportion of 1: mixing the mixture with brominated butyl rubber in a mass ratio of 100, and mixing for 5-20 minutes at 70-110 ℃ to obtain modified brominated butyl rubber;
step S3, in the modified brominated butyl rubber of the step S2, the ratio of 10: adding butyl rubber according to the mass ratio of 90, and banburying at 130-150 ℃ to obtain a rubber main material;
s4, mixing acetylene black and carbon black N330 according to the weight ratio of acetylene black: carbon black N330=2:1, and the carbon black is obtained by uniformly mixing at room temperature;
s5, in a sodium hydroxide solution with the mass fraction of 20%, mixing the components in the ratio of 100:2, adding boron nitrogen polymer, stirring for 40-48 hours at 100-120 ℃, and cleaning and drying to obtain primary treatment boron nitrogen polymer;
s6, in an ethanol solution with the mass fraction of more than 95%, mixing the components in the ratio of 100: adding a silane coupling agent in a mass ratio of 0.05, stirring for 30-50 minutes at 50-60 ℃ to obtain a mixed solution, and mixing the mixed solution according to a ratio of 100: 5, adding the primary treatment boron-nitrogen polymer obtained in the step S5 in a mass ratio, stirring for 18-24 hours at 100-120 ℃, filtering, and drying to obtain a secondary treatment boron-nitrogen polymer;
step S7, mixing the secondary treatment boron-nitrogen polymer obtained in the step S6 with dimethylformamide according to the ratio of 1: 100, adding a silver nitrate solution with the mass fraction of 0.15 percent and the mass ratio of 100:2 to the dimethylformamide after uniformly stirring, mixing and stirring for 1-2 hours at the temperature of 60-80 ℃, standing for 18-24 hours at room temperature, washing and drying to obtain the heat-conducting filler;
step S8, cutting aramid fibers into aramid staple fibers with the length of 2-5 mm, soaking the aramid staple fibers in a dopamine solution with the mass fraction of 2%, keeping the temperature at 65 ℃ for 4 hours, adding a silane coupling agent accounting for 2% of the mass of the dopamine solution, stirring uniformly, keeping the temperature at 65 ℃ for 4 hours, taking out the aramid staple fibers, washing with water and drying to obtain a fiber filler;
step S9, according to castor oil: microcrystalline wax = 5: 1, weighing the processing aid in a mass ratio;
step S10, according to the rubber main materials: carbon black: heat-conducting filler: fiber filler: processing aid = 100: 50: 10: 1: 3, adding the carbon black obtained in the step S4, the heat-conducting filler obtained in the step S7, the fiber filler obtained in the step S8 and the processing aid obtained in the step S9 into the rubber main material obtained in the step S3, and mixing at 130-150 ℃ to prepare a first-stage rubber compound;
step S11, according to the rubber main materials: zinc stearate: stearic acid: zinc oxide: phenolic resin (ortho-methylol content greater than 6%) = 100: 1: 0.2: 5: 2, adding zinc stearate, stearic acid, zinc oxide and phenolic resin into the first-stage rubber compound in the step S10, and mixing at 160-180 ℃ to prepare a second-stage rubber compound;
s12, filtering and tabletting the two-stage rubber compound in the step S11, and curing;
s13, injecting and vulcanizing the two-stage rubber compound cured in the step S12;
and S14, obtaining the heat-conducting curing capsule.
Example 2
This example provides a process for the preparation of a thermally conductive cured capsule, carried out under the same conditions and procedures as in example 1, but with the following adjustments to the formulation:
in step S1, the ratio of phenol: lignin: hydrogen bromide solution = 100: 50: 10 in mass ratio;
in step S2, demethylated lignin is converted to 4: 100 mass ratio with brominated butyl rubber;
in step S3, the modified brominated butyl rubber is prepared by mixing 50: 50 mass percent of butyl rubber is added;
in step S5, the ratio of sodium hydroxide solution with a mass fraction of 20% to sodium hydroxide solution is calculated as 100: 5, adding boron nitrogen macromolecules according to the mass ratio;
in step S6, adding 100 mass percent of ethanol solution with mass fraction of more than 95%: adding a silane coupling agent in a mass ratio of 0.15, and adding the silane coupling agent into the mixed solution according to a ratio of 100: 10, adding a primary treatment boron-nitrogen polymer;
in step S7, mixing the secondary boron nitrogen polymer with dimethylformamide according to the ratio of 5: 100, adding the mixture and dimethylformamide in a mass ratio of 7: 100 of silver nitrate solution with the mass fraction of 0.15 percent;
in step S9, the method comprises the following steps: microcrystalline wax =2: 1.5, weighing the processing aid in a mass ratio;
in step S10, according to rubber main materials: carbon black: heat conductive filler: fiber filler: processing aid = 100: 40: 20: 5: 6.5, preparing a first-stage rubber compound;
in step S11, according to the rubber main materials: zinc acrylate: stearic acid: zinc oxide: phenolic resin (ortho-methylol content greater than 6%) = 100: 5: 0.5: 10: 4, adding zinc acrylate, stearic acid, zinc oxide and phenolic resin to prepare a two-stage rubber compound.
Example 3
This example provides a process for the preparation of a thermally conductive cured capsule, carried out under the same conditions and procedures as in example 1, but with the following adjustments to the formulation:
in step S1, the ratio of phenol: lignin: hydrogen bromide solution = 100: 30: 6, mixing in a mass ratio;
in step S2, demethylated lignin is present in a ratio of 3: 100 mass ratio with brominated butyl rubber;
in step S3, the modified brominated butyl rubber is prepared by mixing 30: 70 of butyl rubber is added;
in step S5, the ratio of sodium hydroxide solution with a mass fraction of 20% to sodium hydroxide solution is calculated as 100: 3, adding boron nitrogen macromolecules according to the mass ratio;
in step S6, adding 100 mass percent of ethanol solution with mass fraction of more than 95%: adding a silane coupling agent in a mass ratio of 0.1, and adding the silane coupling agent into the mixed solution according to a ratio of 100: 8, adding a primary treatment boron-nitrogen polymer;
in step S7, mixing the secondary boron nitrogen polymer with dimethylformamide according to the ratio of 3: 100, adding the mixture and dimethylformamide in a mass ratio of 5: 100 of silver nitrate solution with the mass fraction of 0.15 percent;
in step S9, the method comprises the following steps: microcrystalline wax = 4: 1, weighing the processing aid in a mass ratio;
in step S10, according to rubber main materials: carbon black: heat-conducting filler: fiber filler: processing aid = 100: 45: 15: 3: 4, preparing a first-stage rubber compound;
in step S11, according to rubber main materials: zinc stearate: stearic acid: zinc oxide: phenolic resin (ortho-methylol content greater than 6%) = 100: 3: 0.3: 7: 3, adding zinc stearate, stearic acid, zinc oxide and phenolic resin to prepare a second-stage rubber compound.
Comparative example 1
This comparative example provides a method of preparing a thermally conductive curing bladder, without the use of a thermally conductive filler, as compared to example 1, comprising the steps of:
step S1. add phenol: lignin: hydrogen bromide solution = 100: 10: 2, mixing phenol, lignin and a hydrogen bromide solution with the mass fraction of 45%, reacting for 1-4 hours in a microwave at the temperature of 80-120 ℃, adding water for dilution after the reaction is finished, adjusting the pH value to be =2, centrifuging, washing and drying to obtain demethylated lignin;
step S2, the demethylated lignin obtained in the step S1 is processed according to the proportion of 1: mixing the mixture with brominated butyl rubber in a mass ratio of 100, and mixing for 5-20 minutes at 70-110 ℃ to obtain modified brominated butyl rubber;
step S3, in the modified brominated butyl rubber of the step S2, the ratio of 10: adding butyl rubber according to the mass ratio of 90, and banburying at 130-150 ℃ to obtain a rubber main material;
s4, mixing acetylene black and carbon black N330 according to the weight ratio of acetylene black: carbon black N330=2:1, and the carbon black is obtained by uniformly mixing at room temperature;
step S5, cutting aramid fibers into aramid staple fibers with the length of 2-5 mm, soaking the aramid staple fibers in a dopamine solution with the mass fraction of 2%, keeping the temperature at 65 ℃ for 4 hours, adding a silane coupling agent accounting for 2% of the mass of the dopamine solution, stirring uniformly, keeping the temperature at 65 ℃ for 4 hours, taking out the aramid staple fibers, washing with water and drying to obtain a fiber filler;
s6, according to castor oil: microcrystalline wax = 5: 1, weighing the processing aid in a mass ratio;
step S7, according to the rubber main materials: carbon black: fiber filler: processing aid = 100: 50: 10: 3, adding the carbon black obtained in the step S4, the fiber filler obtained in the step S5 and the processing aid obtained in the step S6 into the rubber main material obtained in the step S3, and mixing at 130-150 ℃ to prepare a first-stage rubber compound;
step S8, according to the rubber main materials: zinc stearate: stearic acid: zinc oxide: phenolic resin (ortho-methylol content greater than 6%) = 100: 1: 0.2: 5: 2, adding zinc stearate, stearic acid, zinc oxide and phenolic resin into the first-stage rubber compound in the step S7, and mixing at 160-180 ℃ to prepare a second-stage rubber compound;
s9, filtering and tabletting the two-stage rubber compound in the step S8, and curing;
s10, injecting and vulcanizing the two-stage rubber compound cured in the step S9;
and S11, obtaining the heat conduction vulcanization capsule.
Comparative example 2
The comparative example provides a preparation method of a heat-conducting curing capsule, and compared with example 1, the method has the advantages that the method adopts butyl rubber as a main rubber material and comprises the following steps:
step S1, mixing acetylene black and carbon black N330 according to the ratio of acetylene black: carbon black N330=2:1, and the carbon black is obtained by uniformly mixing at room temperature;
s2, in a sodium hydroxide solution with the mass fraction of 20%, mixing the components in the ratio of 100:2, adding boron nitrogen macromolecules in a mass ratio, stirring for 40-48 hours at 100-120 ℃, and cleaning and drying to obtain primary treatment boron nitrogen macromolecules;
s3, in an ethanol solution with the mass fraction of more than 95%, mixing the components in the ratio of 100: adding a silane coupling agent in a mass ratio of 0.05, stirring for 30-50 minutes at 50-60 ℃ to obtain a mixed solution, and mixing the mixed solution according to a ratio of 100: 5, adding the primary treatment boron nitrogen polymer obtained in the step S5 in a mass ratio, stirring at 100-120 ℃ for 18-24 hours, filtering, and drying to obtain a secondary treatment boron nitrogen polymer;
step S4, mixing the secondary treatment boron-nitrogen polymer obtained in the step S3 with dimethylformamide according to the ratio of 1: 100, adding a silver nitrate solution with the mass fraction of 0.15 percent and the mass ratio of 100:2 to the dimethylformamide after uniformly stirring, mixing and stirring for 1-2 hours at the temperature of 60-80 ℃, standing for 18-24 hours at room temperature, washing and drying to obtain the heat-conducting filler;
step S5, cutting aramid fibers into aramid staple fibers with the length of 2-5 mm, soaking the aramid staple fibers in a dopamine solution with the mass fraction of 2%, keeping the temperature at 65 ℃ for 4 hours, adding a silane coupling agent accounting for 2% of the mass of the dopamine solution, stirring uniformly, keeping the temperature at 65 ℃ for 4 hours, taking out the aramid staple fibers, washing with water and drying to obtain a fiber filler;
s6, according to castor oil: microcrystalline wax = 5: 1, weighing the processing aid in a mass ratio;
step S7, according to the weight ratio of butyl rubber: carbon black: heat-conducting filler: fiber filler: processing aid = 100: 50: 10: 1: 3, adding the carbon black obtained in the step S1, the heat-conducting filler obtained in the step S4, the fibrous filler obtained in the step S5 and the processing aid obtained in the step S6 into butyl rubber, and mixing at 130-150 ℃ to prepare a first-stage rubber compound;
step S8, according to the weight ratio of butyl rubber: zinc stearate: stearic acid: zinc oxide: phenolic resin (ortho-methylol content greater than 6%) = 100: 1: 0.2: 5: 2, adding zinc stearate, stearic acid, zinc oxide and phenolic resin into the first-stage rubber compound in the step S10, and mixing at 160-180 ℃ to prepare a second-stage rubber compound;
s9, filtering and tabletting the two-stage rubber compound in the step S8, and curing;
s10, injecting and vulcanizing the two-stage rubber compound cured in the step S9;
and S11, obtaining the heat-conducting curing bladder.
Comparative example 3
Compared with the embodiment 1, the preparation method of the heat-conducting curing capsule has the advantages that the rubber main material is butyl rubber alone without using fiber filler, and the preparation method comprises the following steps:
step S1. add phenol: lignin: hydrogen bromide solution = 100: 10: 2, mixing phenol, lignin and a hydrogen bromide solution with the mass fraction of 45%, reacting for 1-4 hours in a microwave at the temperature of 80-120 ℃, adding water for dilution after the reaction is finished, adjusting the pH value to be =2, centrifuging, washing and drying to obtain demethylated lignin;
step S2, the demethylated lignin obtained in the step S1 is processed according to the proportion of 1: mixing the mixture with 100 mass percent of brominated butyl rubber, and mixing for 5-20 minutes at 70-110 ℃ to obtain modified brominated butyl rubber;
step S3, in the modified brominated butyl rubber of the step S2, the ratio of 10: adding butyl rubber according to the mass ratio of 90, and banburying at 130-150 ℃ to obtain a rubber main material;
s4, mixing acetylene black and carbon black N330 according to the weight ratio of acetylene black: carbon black N330=2:1, and the carbon black is obtained by uniformly mixing at room temperature;
s5, in a sodium hydroxide solution with the mass fraction of 20%, mixing the components in the ratio of 100:2, adding boron nitrogen polymer, stirring for 40-48 hours at 100-120 ℃, and cleaning and drying to obtain primary treatment boron nitrogen polymer;
s6, in an ethanol solution with the mass fraction of more than 95%, mixing the components in the ratio of 100: adding a silane coupling agent in a mass ratio of 0.05, stirring for 30-50 minutes at 50-60 ℃ to obtain a mixed solution, and mixing the mixed solution according to a ratio of 100: 5, adding the primary treatment boron-nitrogen polymer obtained in the step S5 in a mass ratio, stirring for 18-24 hours at 100-120 ℃, filtering, and drying to obtain a secondary treatment boron-nitrogen polymer;
step S7, mixing the secondary treatment boron-nitrogen polymer obtained in the step S6 with dimethylformamide according to the ratio of 1: 100, adding a silver nitrate solution with the mass fraction of 0.15 percent and the mass ratio of 100:2 to dimethylformamide after uniformly stirring, mixing and stirring for 1-2 hours at the temperature of 60-80 ℃, standing for 18-24 hours at room temperature, washing and drying to obtain the heat-conducting filler;
step S8, according to castor oil: microcrystalline wax = 5: 1, weighing the processing aid in a mass ratio;
step S9, according to the rubber main materials: carbon black: heat-conducting filler: processing aid = 100: 50: 10: 3, adding the carbon black obtained in the step S4, the heat-conducting filler obtained in the step S7 and the processing aid obtained in the step S8 into the rubber main material obtained in the step S3, and mixing at 130-150 ℃ to prepare a first-stage rubber compound;
step S10, according to the rubber main materials: zinc stearate: stearic acid: zinc oxide: phenolic resin (ortho-methylol content greater than 6%) = 100: 1: 0.2: 5: 2, adding zinc stearate, stearic acid, zinc oxide and phenolic resin into the first-stage rubber compound in the step S9, and mixing at 160-180 ℃ to prepare a second-stage rubber compound;
s11, filtering and tabletting the two-stage rubber compound in the step S10, and curing;
s12, injecting and vulcanizing the two-stage rubber compound cured in the step S11;
and S13, obtaining the heat-conducting curing capsule.
Performance testing
1. Thermal conductivity test
The curing capsules of examples 1-3 and comparative examples 1-3 were tested for thermal conductivity according to standard GB/T11205-2009. A sample to be measured was prepared into a test piece having a length x, a width x and a thickness x of 120mmx60mmx5mm, and the thermal conductivity was measured by a hot wire thermal conductivity measuring instrument at 25 ℃ and a relative humidity of 65%.
2. Tear Strength test
The cured capsules of examples 1-3 and comparative examples 1-3 were tested for tear strength according to the standard GB/T529-2008. A sample to be measured was prepared into a specimen having a length x, a width x and a thickness x of 150mmx20mmx3mm, and a slit having a length of 10mm was cut at a width of 10mm of the specimen in the longitudinal direction by a cutter. The two sides of the cut of the sample were clamped to the clamps of a CSS-44100 electronic universal tester at 25 ℃ respectively, and the tear strength was measured.
3. Tensile Strength and elongation at Break test
The curing capsules of examples 1-3 and comparative examples 1-3 were tested for tensile strength and elongation at break according to the standard GB/T1701-2001. A sample to be tested is cut into a dumbbell-shaped sample with the thickness of 3mm by a standard sample cutter, the sample is clamped on a clamp of a CSS-44100 electronic universal testing machine at the temperature of 25 ℃, and the tensile strength and the elongation at break of the sample are measured.
4.100% -300% stress at definite elongation
The curing capsules of examples 1-3 and comparative examples 1-3 were subjected to a stress at elongation of 100% to 300% according to standard GB/528-2009. A sample to be tested is cut into a dumbbell-shaped sample with the thickness of 2mm by a standard sample cutter, the sample is clamped on a clamp of a CSS-44100 electronic universal testing machine at the temperature of 25 ℃, and the 100-300% stress at definite elongation is measured.
5. Hardness test
The hardness of the cured capsules of examples 1-3 and comparative examples 1-3 was measured using a Shore A durometer at 25 ℃.
The vulcanized capsules of examples 1-3 and comparative examples 1-3 were tested for performance, and the results are shown in Table 1, examples 1-3 and comparative examples 1-3
As can be seen from table 1, the thermal conductivity of the curing bladder of example 1 with the addition of the heat conductive filler is much higher than that of the curing bladder of comparative example 1 without the addition of the heat conductive filler in the same process; the curing bladder of example 1, in which butyl rubber was mixed with the demethylated lignin-modified brominated butyl rubber, had a lower elongation at break than the curing bladder of comparative example 2, in which butyl rubber was used alone in the same process, but had higher mechanical properties than the curing bladder of comparative example 2; the curing bladder of example 1 with the added fibrous filler had a lower elongation at break than the curing bladder of comparative example 3 with no fibrous filler added in the same process, but had higher mechanical properties than comparative example 3; in examples 1 to 3, the thermal conductivity and mechanical strength of the vulcanized capsule were improved with increasing amounts of the heat conductive filler and the fibrous filler, but the elongation at break was slightly decreased.
6. Aging Performance test
The vulcanized capsules of example 1 and comparative examples 1-3 were subjected to performance testing after thermo-oxidative aging at 180 ℃ for 72 hours, the results of which are shown in Table 2,
TABLE 2 Performance test results of example 1 and comparative examples 1-3 after thermo-oxidative aging
As can be seen from Table 2, after thermo-oxidative aging, the vulcanized capsule has small change rate of various performance indexes, and still has good service performance after aging.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents and are included in the scope of the present invention.
Claims (5)
1. A preparation method of a heat-conducting curing capsule is characterized by comprising the following steps:
s100, according to rubber main materials: carbon black: heat-conducting filler: fiber filler: processing aid = 100: (40-50): (10-20): (1-5): (3-6.5) mixing in a mass ratio to prepare a first-stage rubber compound;
s200, adding a coordination aid and a vulcanization aid into the first-stage rubber compound in the step S100, and mixing to prepare a second-stage rubber compound;
s300, filtering and tabletting the two-stage rubber compound in the step S200, and curing;
s400, injecting and vulcanizing the two-stage rubber compound cured in the step S300;
s500, obtaining the heat-conducting curing capsule;
the coordination aid in the step S200 is at least one of zinc stearate and zinc acrylate;
the vulcanization aid in the step S200 comprises stearic acid, zinc oxide and phenolic resin; the ortho-methylol content of the phenolic resin is more than 6 percent;
the rubber main material in the step S100 comprises butyl rubber with low unsaturation degree and modified brominated butyl rubber, wherein the modified brominated butyl rubber is obtained by grafting demethylated lignin to brominated butyl rubber;
the heat-conducting filler is a boron-nitrogen polymer modified by nano silver, and the boron-nitrogen polymer is one or more of hexagonal boron nitride, cubic boron nitride and rhombohedral boron nitride;
the fiber filler in the step S100 is aramid staple fiber treated by dopamine;
the step S100 specifically includes:
step S110, mixing phenol, lignin and a hydrogen bromide solution, reacting for 1-4 hours in a microwave at 80-120 ℃, adding water for dilution after the reaction is finished, adjusting the pH value to be =2, centrifuging, washing and drying to obtain demethylated lignin;
s120, mixing the demethylated lignin obtained in the step S110 with bromobutyl rubber at 70-110 ℃ for 5-20 minutes to obtain modified bromobutyl rubber;
s130, adding butyl rubber into the modified brominated butyl rubber in the step S120, and banburying at 130-150 ℃ to obtain the rubber main material;
s140, uniformly mixing acetylene carbon black and carbon black N330 at room temperature to obtain the carbon black;
s150, adding the boron-nitrogen polymer into a sodium hydroxide solution, stirring for 40-48 hours at 100-120 ℃, and cleaning and drying to obtain a primary treatment boron-nitrogen polymer;
s160, adding a silane coupling agent into an ethanol solution, stirring for 30-50 minutes at 50-60 ℃ to obtain a mixed solution, adding the primary treatment boron-nitrogen polymer obtained in the step S150 into the mixed solution, stirring for 18-24 hours at 100-120 ℃, filtering, and drying to obtain a secondary treatment boron-nitrogen polymer;
s170, mixing the secondary-treatment boron-nitrogen polymer obtained in the step S160 with dimethylformamide, uniformly stirring, adding a silver nitrate solution, mixing and stirring at 60-80 ℃ for 1-2 hours, standing at room temperature for 18-24 hours, washing and drying to obtain the heat-conducting filler;
s180, cutting aramid fibers into aramid staple fibers with the length of 2-5 mm, soaking the aramid staple fibers in a dopamine solution, preserving heat at 65 ℃ for 4 hours, adding a silane coupling agent, uniformly stirring, continuously preserving heat at 65 ℃ for 4 hours, taking out the aramid staple fibers, washing with water, and drying to obtain the fiber filler;
step S190, adding the carbon black obtained in the step S140, the heat-conducting filler obtained in the step S170, the fiber filler obtained in the step S180 and the processing aid obtained in the step S100 into the rubber main material obtained in the step S130, and mixing at 130-150 ℃ to prepare the rubber compound.
2. The method of claim 1, wherein the curing bladder is made of a thermally conductive material,
the mass ratio of the rubber main material in the step S100 to the stearic acid, the zinc oxide and the phenolic resin in the coordination aid and the vulcanization aid in the step S200 is as follows: coordination aid: stearic acid: zinc oxide: phenolic resin = 100: (1-5): (0.2-0.5): (5-10): (2-4); the mixing temperature in the step S100 is 130-150 ℃, and the mixing temperature in the step S200 is 160-180 ℃.
3. The method of claim 1, wherein the processing aid of step S100 comprises castor oil and microcrystalline wax.
4. The method of claim 3, wherein the curing bladder is made of a thermally conductive material,
in step S110, the mass fraction of the hydrogen bromide solution is 45%, and the mass ratio of the phenol to the lignin to the hydrogen bromide solution is phenol: lignin: hydrogen bromide solution = 100: (10-50): (2-10); and/or
In the step S120, the mass ratio of the bromobutyl rubber to the demethylated lignin is bromobutyl rubber: demethylated lignin = 100: (1-40); and/or
In the step S130, the mass ratio of the butyl rubber to the modified brominated butyl rubber is butyl rubber: modified brominated butyl rubber = (50-90): (10-50); and/or
In the step S140, the mass ratio of the acetylene black to the carbon black N330 is acetylene black: carbon black N330=2: 1; and/or
In the step S150, the mass fraction of sodium hydroxide in the sodium hydroxide solution is 20%, and the mass ratio of the sodium hydroxide solution to the boron nitride polymer is: boron nitrogen macromolecule = 100: (2-5); and/or
In the step S160, the mass fraction of ethanol in the ethanol solution is greater than 95%, and the mass ratio of the ethanol solution to the silane coupling agent is: silane coupling agent = 100: (0.05-0.15); the mass ratio of the mixed solution to the boron-nitrogen polymer subjected to primary treatment is mixed solution: primary treatment of boron nitrogen polymer = 100: (5-10); and/or
In the step S170, the mass fraction of silver nitrate in the silver nitrate solution is 0.15%, and the mass ratio of the dimethylformamide, the secondarily processed boron-nitrogen polymer, and the silver nitrate solution is dimethylformamide: secondary treatment of boron-nitrogen polymer: silver nitrate solution = 100: (1-5): (2-7); and/or
In the step S180, the dopamine accounts for 2% by mass of the dopamine solution, and the silane coupling agent accounts for 2% by mass of the dopamine solution; and/or
In the step S190, the mass ratio of the castor oil to the microcrystalline wax in the processing aid is castor oil: microcrystalline wax = (2-5): (1-1.5).
5. A heat-conducting vulcanized capsule, which is characterized by being prepared by the preparation method of the heat-conducting vulcanized capsule as claimed in any one of claims 1 to 4.
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|---|---|---|---|---|
| GB930990A (en) * | 1958-10-20 | 1963-07-10 | West Virginia Pulp & Paper Co | Lignin resins and preparations thereof |
| CN110652971A (en) * | 2019-11-01 | 2020-01-07 | 中国林业科学研究院林产化学工业研究所 | Modified nano lignin and preparation method and application thereof |
| CN111393593A (en) * | 2020-03-03 | 2020-07-10 | 南京工业大学 | Demethylated lignin liquid modified phenolic resin, preparation method thereof and application thereof in phenolic foam |
| CN111748133A (en) * | 2020-07-08 | 2020-10-09 | 南京工业大学 | Application of lignin in preparation of radial tires |
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2020
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB930990A (en) * | 1958-10-20 | 1963-07-10 | West Virginia Pulp & Paper Co | Lignin resins and preparations thereof |
| CN110652971A (en) * | 2019-11-01 | 2020-01-07 | 中国林业科学研究院林产化学工业研究所 | Modified nano lignin and preparation method and application thereof |
| CN111393593A (en) * | 2020-03-03 | 2020-07-10 | 南京工业大学 | Demethylated lignin liquid modified phenolic resin, preparation method thereof and application thereof in phenolic foam |
| CN111748133A (en) * | 2020-07-08 | 2020-10-09 | 南京工业大学 | Application of lignin in preparation of radial tires |
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