CN116063721A - Fluororubber sealing material resistant to sodium ion battery electrolyte and preparation method thereof - Google Patents

Fluororubber sealing material resistant to sodium ion battery electrolyte and preparation method thereof Download PDF

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Publication number
CN116063721A
CN116063721A CN202310156286.1A CN202310156286A CN116063721A CN 116063721 A CN116063721 A CN 116063721A CN 202310156286 A CN202310156286 A CN 202310156286A CN 116063721 A CN116063721 A CN 116063721A
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fluororubber
sealing material
stirring
ion battery
sodium ion
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CN116063721B (en
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敖煜之
程亚南
简鹏
朱翔
刘珊
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Jiangsu Zhongyu Rubber Plastic Technology Co ltd
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Jiangsu Zhongyu Rubber Plastic Technology Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • 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
    • C08K3/02—Elements
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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
    • C08K3/34—Silicon-containing compounds
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Sealing Material Composition (AREA)

Abstract

The invention relates to the technical field of rubber materials, in particular to a fluororubber sealing material of sodium ion battery electrolyte and a preparation method thereof. The electrolyte performance of the sodium ion resistant battery of the fluororubber sealing material is enhanced, so that the fluororubber sealing material has good corrosion resistance and hardness, and meets the industrial production requirement.

Description

Fluororubber sealing material resistant to sodium ion battery electrolyte and preparation method thereof
Technical Field
The invention relates to the technical field of rubber materials, in particular to a fluororubber sealing material resistant to sodium ion battery electrolyte and a preparation method thereof.
Background
With the development of society and technology, fluororubbers are widely used in industrial, agricultural, civil and military fields, and a large amount of solutions such as acid, alkali and the like are contained and used in a use environment, which can damage the rubber over time. Sodium hexafluorophosphate is needed to be added into the electrolyte of the sodium ion battery as electrolyte, and is very sensitive to the moisture content and easy to decompose to generate hydrofluoric acid, and the hydrofluoric acid can react with rubber to corrode the rubber. The prior fluororubber has poor corrosion resistance, is easy to be corroded by hydrofluoric acid, and affects the service life of products, thereby affecting the normal operation of the work.
In order to solve the problems, the invention provides a fluororubber sealing material resistant to sodium ion battery electrolyte and a preparation method thereof.
Disclosure of Invention
The invention aims to provide a fluororubber sealing material resistant to sodium ion battery electrolyte and a preparation method thereof, so as to solve the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme:
a preparation method of fluororubber sealing material resistant to sodium ion battery electrolyte comprises the following steps:
step one: taking basalt and sodium hydroxide solution, reacting for 2-3 hours, filtering, washing, adding deionized water, uniformly stirring, adding bis- (triethoxysilylpropyl) -tetrasulfide, stirring for 1-2 hours, adding phosphoric acid, reacting for 8-10 hours, and washing; adding deionized water, stirring uniformly, adding polysiloxane, stirring at 75-80 ℃ for reaction for 7-9h, filtering, and washing to obtain modified basalt;
step two: taking the epoxy resin coating and the dimethylbenzene, uniformly stirring, adding the corrosion inhibitor and the modified basalt, continuously stirring for 30-40min, adding the curing agent, and uniformly stirring to obtain the anti-corrosion coating;
step three: placing fluororubber on an open mill, pressing for 2-4min, adding processing aid, vulcanizing agent, reinforcing filler and active agent, mixing, and discharging to obtain a mixed rubber; taking the rubber compound, carrying out primary vulcanization, taking out, carrying out secondary vulcanization to obtain a fluororubber material, coating an anticorrosive paint on the surface of the fluororubber material, and curing for 40-60min to obtain the fluororubber sealing material.
More preferably, in the first step, the preparation method of the polysiloxane comprises the following steps: mixing KH-550 and deionized water, stirring, adding concentrated hydrochloric acid, adjusting pH, reacting at 50-55deg.C for 3-5 hr, evaporating solvent, and drying to obtain polysiloxane.
More optimally, in the second step, the preparation method of the corrosion inhibitor comprises the following steps:
mixing emulsifier, cyclohexane and ammonia water, and stirring to obtain oil phase; mixing benzotriazole and deionized water, stirring uniformly, and performing ultrasonic treatment for 10-15min to obtain a water phase; dropwise adding the water phase into the oil phase under stirring for 60-70min to form emulsion, dropwise adding ethyl orthosilicate for 60-70min, reacting for 22-26h, demulsifying, centrifuging, separating, and drying to obtain the corrosion inhibitor.
More preferably, the fluororubber material comprises the following components in weight: 100-120 parts of fluororubber, 2-4 parts of processing aid, 2-4 parts of vulcanizing agent, 20-25 parts of reinforcing filler and 4-7 parts of active agent.
More preferably, the processing aid is any one or more of sodium stearate and zinc stearate.
More preferably, the vulcanizing agent is di-t-butylperoxy-diisopropylbenzene.
More preferably, the reinforcing filler is nano carbon black; the nanometer carbon black is any one or more of nanometer carbon black N330, nanometer carbon black N550 and nanometer carbon black N990.
More preferably, the active agent is triallyl cyanurate.
More preferably, in the third step, the conditions of primary vulcanization are as follows: the temperature is 175-185 ℃ and the vulcanizing time is 10-15min; the secondary vulcanization conditions are as follows: the temperature is 200-230 ℃ and the vulcanizing time is 10-12h.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, the surface of the fluororubber is coated with the anticorrosive paint, the basalt is modified by using the bis- (triethoxysilylpropyl) -tetrasulfide, and the polysulfide group on the modified basalt can react with double bonds in the fluororubber during thermal curing, so that the interface compatibility between the anticorrosive paint and the fluororubber material is improved, after phosphoric acid is added, the reaction time is controlled to be 8-10h, partial hydroxyl groups are reserved on the basalt, so that the basalt can further react with polysiloxane, amino groups are grafted on the basalt, and the amino groups react with epoxy groups on the epoxy resin, so that the compatibility between the basalt and the epoxy groups is improved, and the performance of the sodium ion resistant battery electrolyte of the fluororubber sealing material is enhanced.
(2) The invention also uses benzotriazole as a corrosion inhibitor and loads the benzotriazole into the silicon dioxide, and simultaneously, silicon hydroxyl on the silicon dioxide can react with amino groups on basalt, so that the compatibility between the silicon hydroxyl and the basalt is good, the dispersibility of the corrosion inhibitor in epoxy resin is enhanced, and the corrosion resistance of the fluororubber sealing material is further enhanced.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Step one: taking 40-gKH-550 mL of deionized water, uniformly stirring, adding concentrated hydrochloric acid, adjusting the pH value to 5, reacting for 4 hours at 53 ℃, evaporating the solvent, and drying to obtain polysiloxane.
Step two: preparation of modified basalt:
taking 10g basalt and 800mL of 5mol/L sodium hydroxide solution, reacting for 2.5h, filtering, washing, adding 300mL of deionized water, uniformly stirring, adding 6mL of bis- (triethoxysilylpropyl) -tetrasulfide, stirring for 1.5h, adding 2mL of phosphoric acid, reacting for 9h, and washing; adding 300mL of deionized water, uniformly stirring, adding 12mL of polysiloxane, stirring at 78 ℃ for reaction for 8h, filtering, and washing to obtain the modified basalt.
Bis- (triethoxysilylpropyl) -tetrasulfide was purchased from Kain chemical.
Step three: preparation of corrosion inhibitor:
1g of emulsifier OP-10, 8g of emulsifier Span80, 100mL of cyclohexane and 4mL of ammonia water are taken and uniformly stirred to obtain an oil phase; taking 2g of benzotriazole and 120mL of deionized water, uniformly stirring, and carrying out ultrasonic treatment for 12min to obtain a water phase; dropwise adding the water phase into the oil phase under stirring for 65min to form emulsion, dropwise adding 30mL of ethyl orthosilicate for 65min, reacting for 25h, demulsifying, centrifugally separating, and drying to obtain the corrosion inhibitor.
Step four: preparation of the anticorrosive paint:
100g of epoxy resin paint and 25g of dimethylbenzene are taken and stirred uniformly, 2g of corrosion inhibitor and 3g of modified basalt are added, stirring is continued for 35min, 30g of T31 curing agent is added, and stirring is uniform, so that the anticorrosive paint is obtained.
Epoxy resin paint was purchased from Guangdong Co., ltd
T31 curing agent is purchased from Guangdong applied anti-corrosion technology Co., ltd;
step five: preparation of fluororubber sealing material:
placing fluororubber on an open mill, pressing for 3min, adding processing aid sodium stearate, vulcanizing agent di-tert-butylperoxy-diisopropylbenzene, reinforcing filler nano carbon black N330 and active agent triallyl cyanurate, mixing, and discharging slices to obtain a mixed rubber; taking the rubber compound for primary vulcanization, wherein the temperature is 180 ℃ and the vulcanization time is 12min; taking out, performing secondary vulcanization, wherein the temperature is 220 ℃, and the vulcanization time is 11 hours, so as to obtain the fluororubber material, coating the surface of the fluororubber material with an anti-corrosion coating, curing for 50 minutes, and obtaining the fluororubber sealing material, wherein the thickness of the coating is 20 mu m.
The fluororubber material comprises the following components in parts by weight: 110 parts of fluororubber, 3 parts of processing aid sodium stearate, 3 parts of vulcanizing agent di-tert-butylperoxy-diisopropylbenzene, 23 parts of reinforcing filler nano carbon black N330 and 5 parts of active agent triallyl cyanurate.
Example 2
Step one: taking 40-gKH-550 mL of deionized water, uniformly stirring, adding concentrated hydrochloric acid, adjusting the pH value to 5, reacting for 3 hours at 50 ℃, evaporating the solvent, and drying to obtain polysiloxane.
Step two: preparation of modified basalt:
taking 10g basalt and 800mL of 5mol/L sodium hydroxide solution, reacting for 2 hours, filtering, washing, adding 300mL of deionized water, uniformly stirring, adding 6mL of bis- (triethoxysilylpropyl) -tetrasulfide, stirring for 1 hour, adding 2mL of phosphoric acid, reacting for 8 hours, and washing; adding 300mL of deionized water, uniformly stirring, adding 12mL of polysiloxane, stirring at 75 ℃ for reaction for 7h, filtering, and washing to obtain the modified basalt.
Bis- (triethoxysilylpropyl) -tetrasulfide was purchased from Kain chemical.
Step three: preparation of corrosion inhibitor:
1g of emulsifier OP-10, 8g of emulsifier Span80, 100mL of cyclohexane and 4mL of ammonia water are taken and uniformly stirred to obtain an oil phase; taking 2g of benzotriazole and 120mL of deionized water, uniformly stirring, and carrying out ultrasonic treatment for 10min to obtain a water phase; dropwise adding the water phase into the oil phase under stirring for 60min to form emulsion, dropwise adding 30mL of ethyl orthosilicate for 60min, reacting for 22h, demulsifying, centrifugally separating, and drying to obtain the corrosion inhibitor.
Step four: preparation of the anticorrosive paint:
100g of epoxy resin paint and 25g of dimethylbenzene are taken and stirred uniformly, 2g of corrosion inhibitor and 3g of modified basalt are added, stirring is continued for 30min, 30g of T31 curing agent is added, and stirring is uniform, so that the anticorrosive paint is obtained.
Epoxy resin paint was purchased from Guangdong Co., ltd
T31 curing agent is purchased from Guangdong applied anti-corrosion technology Co., ltd;
step five: preparation of fluororubber sealing material:
placing fluororubber on an open mill, pressing for 2min, adding a processing aid zinc stearate, a vulcanizing agent di-tert-butylperoxy-diisopropylbenzene, a reinforcing filler nano carbon black N550 and an active agent triallyl cyanurate, mixing, and discharging slices to obtain a mixed rubber; taking the rubber compound for primary vulcanization, wherein the temperature is 175 ℃ and the vulcanization time is 10min; taking out, performing secondary vulcanization, wherein the temperature is 200 ℃ and the vulcanization time is 10 hours, so as to obtain the fluororubber material, coating the surface of the fluororubber material with the anti-corrosion coating, curing for 40 minutes, and obtaining the fluororubber sealing material, wherein the thickness of the coating is 20 mu m.
The fluororubber material comprises the following components in parts by weight: 100 parts of fluororubber, 2 parts of processing aid zinc stearate, 2 parts of vulcanizing agent di-tert-butylperoxy-diisopropylbenzene, 20 parts of reinforcing filler nano carbon black N550 and 4 parts of active agent triallyl cyanurate.
Example 3
Step one: taking 40-gKH-550 mL of deionized water, uniformly stirring, adding concentrated hydrochloric acid, adjusting the pH value to 5, reacting for 5 hours at 55 ℃, evaporating the solvent, and drying to obtain polysiloxane.
Step two: preparation of modified basalt:
taking 10g basalt and 800mL of 5mol/L sodium hydroxide solution, reacting for 3 hours, filtering, washing, adding 300mL of deionized water, uniformly stirring, adding 6mL of bis- (triethoxysilylpropyl) -tetrasulfide, stirring for 2 hours, adding 2mL of phosphoric acid, reacting for 10 hours, and washing; adding 300mL of deionized water, uniformly stirring, adding 12mL of polysiloxane, stirring at 80 ℃ for reaction for 9h, filtering, and washing to obtain the modified basalt.
Bis- (triethoxysilylpropyl) -tetrasulfide was purchased from Kain chemical.
Step three: preparation of corrosion inhibitor:
1g of emulsifier OP-10, 8g of emulsifier Span80, 100mL of cyclohexane and 4mL of ammonia water are taken and uniformly stirred to obtain an oil phase; taking 2g of benzotriazole and 120mL of deionized water, uniformly stirring, and carrying out ultrasonic treatment for 15min to obtain a water phase; dropwise adding the water phase into the oil phase under stirring for 70min to form emulsion, dropwise adding 30mL of ethyl orthosilicate for 70min, reacting for 26h, demulsifying, centrifugally separating, and drying to obtain the corrosion inhibitor.
Step four: preparation of the anticorrosive paint:
100g of epoxy resin paint and 25g of dimethylbenzene are taken and stirred uniformly, 2g of corrosion inhibitor and 3g of modified basalt are added, stirring is continued for 40min, 30g of T31 curing agent is added, and stirring is uniform, so that the anticorrosive paint is obtained.
Epoxy resin paint was purchased from Guangdong Co., ltd
T31 curing agent is purchased from Guangdong applied anti-corrosion technology Co., ltd;
step five: preparation of fluororubber sealing material:
placing fluororubber on an open mill, pressing for 4min, adding processing aid sodium stearate, vulcanizing agent di-tert-butylperoxy-diisopropylbenzene, reinforcing filler nano carbon black N990 and active agent triallyl cyanurate, mixing, and discharging slices to obtain a mixed rubber; taking the rubber compound for primary vulcanization at 185 ℃ for 15min; taking out, performing secondary vulcanization, wherein the temperature is 230 ℃ and the vulcanization time is 12 hours, so as to obtain the fluororubber material, coating the surface of the fluororubber material with the anti-corrosion coating, curing for 60 minutes, and obtaining the fluororubber sealing material, wherein the thickness of the coating is 20 mu m.
The fluororubber material comprises the following components in parts by weight: 120 parts of fluororubber, 4 parts of processing aid sodium stearate, 4 parts of vulcanizing agent di-tert-butylperoxy-diisopropylbenzene, 25 parts of reinforcing filler nano carbon black N990 and 7 parts of active agent triallyl cyanurate.
Example 4: basalt was modified without bis- (triethoxysilylpropyl) -tetrasulfide, and the rest was the same as in example 1.
Step one: taking 40-gKH-550 mL of deionized water, uniformly stirring, adding concentrated hydrochloric acid, adjusting the pH value to 5, reacting for 4 hours at 53 ℃, evaporating the solvent, and drying to obtain polysiloxane.
Step two: preparation of modified basalt:
taking 10g basalt and 800mL sodium hydroxide solution with the concentration of 5mol/L, reacting for 2.5 hours, filtering, washing, adding 300mL deionized water, uniformly stirring, adding 12mL polysiloxane, stirring at 78 ℃ for reacting for 8 hours, filtering, and washing to obtain the modified basalt.
Step three: preparation of corrosion inhibitor:
1g of emulsifier OP-10, 8g of emulsifier Span80, 100mL of cyclohexane and 4mL of ammonia water are taken and uniformly stirred to obtain an oil phase; taking 2g of benzotriazole and 120mL of deionized water, uniformly stirring, and carrying out ultrasonic treatment for 12min to obtain a water phase; dropwise adding the water phase into the oil phase under stirring for 65min to form emulsion, dropwise adding 30mL of ethyl orthosilicate for 65min, reacting for 25h, demulsifying, centrifugally separating, and drying to obtain the corrosion inhibitor.
Step four: preparation of the anticorrosive paint:
100g of epoxy resin paint and 25g of dimethylbenzene are taken and stirred uniformly, 2g of corrosion inhibitor and 3g of modified basalt are added, stirring is continued for 35min, 30g of T31 curing agent is added, and stirring is uniform, so that the anticorrosive paint is obtained.
Epoxy resin paint was purchased from Guangdong Co., ltd
T31 curing agent is purchased from Guangdong applied anti-corrosion technology Co., ltd;
step five: preparation of fluororubber sealing material:
placing fluororubber on an open mill, pressing for 3min, adding processing aid sodium stearate, vulcanizing agent di-tert-butylperoxy-diisopropylbenzene, reinforcing filler nano carbon black N330 and active agent triallyl cyanurate, mixing, and discharging slices to obtain a mixed rubber; taking the rubber compound for primary vulcanization, wherein the temperature is 180 ℃ and the vulcanization time is 12min; taking out, performing secondary vulcanization, wherein the temperature is 220 ℃, and the vulcanization time is 11 hours, so as to obtain the fluororubber material, coating the surface of the fluororubber material with an anti-corrosion coating, curing for 50 minutes, and obtaining the fluororubber sealing material, wherein the thickness of the coating is 20 mu m.
The fluororubber material comprises the following components in parts by weight: 110 parts of fluororubber, 3 parts of processing aid sodium stearate, 3 parts of vulcanizing agent di-tert-butylperoxy-diisopropylbenzene, 23 parts of reinforcing filler nano carbon black N330 and 5 parts of active agent triallyl cyanurate.
Example 5: polysiloxane was not added, and the rest was the same as in example 1.
Step one: preparation of modified basalt:
taking 10g basalt and 800mL sodium hydroxide solution with the concentration of 5mol/L, reacting for 2.5h, filtering, washing, adding 300mL deionized water, uniformly stirring, adding 6mL bis- (triethoxysilylpropyl) -tetrasulfide, stirring for 1.5h, adding 2mL phosphoric acid, reacting for 9h, and washing to obtain the modified basalt.
Bis- (triethoxysilylpropyl) -tetrasulfide was purchased from Kain chemical.
Step two: preparation of corrosion inhibitor:
1g of emulsifier OP-10, 8g of emulsifier Span80, 100mL of cyclohexane and 4mL of ammonia water are taken and uniformly stirred to obtain an oil phase; taking 2g of benzotriazole and 120mL of deionized water, uniformly stirring, and carrying out ultrasonic treatment for 12min to obtain a water phase; dropwise adding the water phase into the oil phase under stirring for 65min to form emulsion, dropwise adding 30mL of ethyl orthosilicate for 65min, reacting for 25h, demulsifying, centrifugally separating, and drying to obtain the corrosion inhibitor.
Step three: preparation of the anticorrosive paint:
100g of epoxy resin paint and 25g of dimethylbenzene are taken and stirred uniformly, 2g of corrosion inhibitor and 3g of modified basalt are added, stirring is continued for 35min, 30g of T31 curing agent is added, and stirring is uniform, so that the anticorrosive paint is obtained.
Epoxy resin paint was purchased from Guangdong Co., ltd
T31 curing agent is purchased from Guangdong applied anti-corrosion technology Co., ltd;
step four: preparation of fluororubber sealing material:
placing fluororubber on an open mill, pressing for 3min, adding processing aid sodium stearate, vulcanizing agent di-tert-butylperoxy-diisopropylbenzene, reinforcing filler nano carbon black N330 and active agent triallyl cyanurate, mixing, and discharging slices to obtain a mixed rubber; taking the rubber compound for primary vulcanization, wherein the temperature is 180 ℃ and the vulcanization time is 12min; taking out, performing secondary vulcanization, wherein the temperature is 220 ℃, and the vulcanization time is 11 hours, so as to obtain the fluororubber material, coating the surface of the fluororubber material with an anti-corrosion coating, curing for 50 minutes, and obtaining the fluororubber sealing material, wherein the thickness of the coating is 20 mu m.
The fluororubber material comprises the following components in parts by weight: 110 parts of fluororubber, 3 parts of processing aid sodium stearate, 3 parts of vulcanizing agent di-tert-butylperoxy-diisopropylbenzene, 23 parts of reinforcing filler nano carbon black N330 and 5 parts of active agent triallyl cyanurate.
Example 6: after the phosphoric acid was added, the reaction time was controlled to 20 hours, and the rest was the same as in example 1.
Step one: taking 40-gKH-550 mL of deionized water, uniformly stirring, adding concentrated hydrochloric acid, adjusting the pH value to 5, reacting for 4 hours at 53 ℃, evaporating the solvent, and drying to obtain polysiloxane.
Step two: preparation of modified basalt:
taking 10g basalt and 800mL of 5mol/L sodium hydroxide solution, reacting for 2.5h, filtering, washing, adding 300mL of deionized water, uniformly stirring, adding 6mL of bis- (triethoxysilylpropyl) -tetrasulfide, stirring for 1.5h, adding 2mL of phosphoric acid, reacting for 20h, and washing; adding 300mL of deionized water, uniformly stirring, adding 12mL of polysiloxane, stirring at 78 ℃ for reaction for 8h, filtering, and washing to obtain the modified basalt.
Bis- (triethoxysilylpropyl) -tetrasulfide was purchased from Kain chemical.
Step three: preparation of corrosion inhibitor:
1g of emulsifier OP-10, 8g of emulsifier Span80, 100mL of cyclohexane and 4mL of ammonia water are taken and uniformly stirred to obtain an oil phase; taking 2g of benzotriazole and 120mL of deionized water, uniformly stirring, and carrying out ultrasonic treatment for 12min to obtain a water phase; dropwise adding the water phase into the oil phase under stirring for 65min to form emulsion, dropwise adding 30mL of ethyl orthosilicate for 65min, reacting for 25h, demulsifying, centrifugally separating, and drying to obtain the corrosion inhibitor.
Step four: preparation of the anticorrosive paint:
100g of epoxy resin paint and 25g of dimethylbenzene are taken and stirred uniformly, 2g of corrosion inhibitor and 3g of modified basalt are added, stirring is continued for 35min, 30g of T31 curing agent is added, and stirring is uniform, so that the anticorrosive paint is obtained.
Epoxy resin paint was purchased from Guangdong Co., ltd
T31 curing agent is purchased from Guangdong applied anti-corrosion technology Co., ltd;
step five: preparation of fluororubber sealing material:
placing fluororubber on an open mill, pressing for 3min, adding processing aid sodium stearate, vulcanizing agent di-tert-butylperoxy-diisopropylbenzene, reinforcing filler nano carbon black N330 and active agent triallyl cyanurate, mixing, and discharging slices to obtain a mixed rubber; taking the rubber compound for primary vulcanization, wherein the temperature is 180 ℃ and the vulcanization time is 12min; taking out, performing secondary vulcanization, wherein the temperature is 220 ℃, and the vulcanization time is 11 hours, so as to obtain the fluororubber material, coating the surface of the fluororubber material with an anti-corrosion coating, curing for 50 minutes, and obtaining the fluororubber sealing material, wherein the thickness of the coating is 20 mu m.
The fluororubber material comprises the following components in parts by weight: 110 parts of fluororubber, 3 parts of processing aid sodium stearate, 3 parts of vulcanizing agent di-tert-butylperoxy-diisopropylbenzene, 23 parts of reinforcing filler nano carbon black N330 and 5 parts of active agent triallyl cyanurate.
Experiment:
taking the fluororubber sealing materials prepared in the examples 1 to 6, performing performance test at 25 ℃, and testing the hardness of the fluororubber sealing material according to GB/T531-2008; the fluororubber sealing material was tested for corrosion resistance according to GB/T1690-2006, and the data obtained are shown in the following table:
Figure BDA0004092474530000091
conclusion: from the above data, it is clear that the modification of basalt using bis- (triethoxysilylpropyl) -tetrasulfide is not performed in example 4, and the effect of hydrofluoric acid is large and the corrosion resistance is lowered. Example 5 without polysiloxane addition, the effect of hydrofluoric acid was greater. Example 6 after phosphoric acid was added, the reaction time was controlled to 20 hours, the grafted bis- (triethoxysilylpropyl) -tetrasulfide became more, the hydroxyl groups remained on basalt became less, the grafted amine groups became less, the performance became worse, and the resistance to hydrofluoric acid corrosion became worse.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A preparation method of a fluororubber sealing material resistant to sodium ion battery electrolyte is characterized by comprising the following steps: the method comprises the following steps:
step one: taking basalt and sodium hydroxide solution, reacting for 2-3 hours, filtering, washing, adding deionized water, uniformly stirring, adding bis- (triethoxysilylpropyl) -tetrasulfide, stirring for 1-2 hours, adding phosphoric acid, reacting for 8-10 hours, and washing; adding deionized water, stirring uniformly, adding polysiloxane, stirring at 75-80 ℃ for reaction for 7-9h, filtering, and washing to obtain modified basalt;
step two: taking the epoxy resin coating and the dimethylbenzene, uniformly stirring, adding the corrosion inhibitor and the modified basalt, continuously stirring for 30-40min, adding the curing agent, and uniformly stirring to obtain the anti-corrosion coating;
step three: placing fluororubber on an open mill, pressing for 2-4min, adding processing aid, vulcanizing agent, reinforcing filler and active agent, mixing, and discharging to obtain a mixed rubber; taking the rubber compound, carrying out primary vulcanization, taking out, carrying out secondary vulcanization to obtain a fluororubber material, coating an anticorrosive paint on the surface of the fluororubber material, and curing for 40-60min to obtain the fluororubber sealing material.
2. The method for preparing the fluororubber sealing material for the sodium ion battery electrolyte, according to claim 1, is characterized in that: in the first step, the preparation method of the polysiloxane comprises the following steps: mixing KH-550 and deionized water, stirring, adding concentrated hydrochloric acid, adjusting pH, reacting at 50-55deg.C for 3-5 hr, evaporating solvent, and drying to obtain polysiloxane.
3. The method for preparing the fluororubber sealing material for the sodium ion battery electrolyte, according to claim 1, is characterized in that: in the second step, the preparation method of the corrosion inhibitor comprises the following steps:
mixing emulsifier, cyclohexane and ammonia water, and stirring to obtain oil phase; mixing benzotriazole and deionized water, stirring uniformly, and performing ultrasonic treatment for 10-15min to obtain a water phase; dropwise adding the water phase into the oil phase under stirring for 60-70min to form emulsion, dropwise adding ethyl orthosilicate for 60-70min, reacting for 22-26h, demulsifying, centrifuging, separating, and drying to obtain the corrosion inhibitor.
4. The method for preparing the fluororubber sealing material for the sodium ion battery electrolyte, according to claim 1, is characterized in that: the fluororubber material comprises the following components in parts by weight: 100-120 parts of fluororubber, 2-4 parts of processing aid, 2-4 parts of vulcanizing agent, 20-25 parts of reinforcing filler and 4-7 parts of active agent.
5. The method for preparing the fluororubber sealing material for the sodium ion battery electrolyte, which is characterized by comprising the following steps of: the processing aid is any one or more of sodium stearate and zinc stearate.
6. The method for preparing the fluororubber sealing material for the sodium ion battery electrolyte, which is characterized by comprising the following steps of: the vulcanizing agent is di-tert-butylperoxy-diisopropylbenzene.
7. The method for preparing the fluororubber sealing material for the sodium ion battery electrolyte, which is characterized by comprising the following steps of: the reinforcing filler is nano carbon black; the nanometer carbon black is any one or more of nanometer carbon black N330, nanometer carbon black N550 and nanometer carbon black N990.
8. The method for preparing the fluororubber sealing material for the sodium ion battery electrolyte, which is characterized by comprising the following steps of: the active agent is triallyl cyanurate.
9. The method for preparing the fluororubber sealing material for the sodium ion battery electrolyte, according to claim 1, is characterized in that: in the third step, the conditions of primary vulcanization are as follows: the temperature is 175-185 ℃ and the vulcanizing time is 10-15min; the secondary vulcanization conditions are as follows: the temperature is 200-230 ℃ and the vulcanizing time is 10-12h.
10. The fluororubber sealing material for sodium ion battery electrolyte prepared by the method for preparing the fluororubber sealing material for sodium ion battery electrolyte according to any one of claims 1-9.
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013147561A (en) * 2012-01-19 2013-08-01 Yokohama Rubber Co Ltd:The Rubber composition for tire and pneumatic tire using the same
CN105175783A (en) * 2015-10-10 2015-12-23 青岛科技大学 Surface treatment method for continuous basalt fiber framework material
CN106117670A (en) * 2016-07-06 2016-11-16 无锡宝通科技股份有限公司 A kind of resistance to calcination anti tear conveyer belt coating rubber and preparation method thereof
CN107352218A (en) * 2017-06-02 2017-11-17 浙江龙圣华橡胶有限公司 A kind of preparation method of basalt fibre canvas core conveyor belt
CN109486143A (en) * 2018-10-29 2019-03-19 安徽汇创新材料有限公司 A kind of septic tank heat resistant glass Steel material
JP2019182920A (en) * 2018-04-03 2019-10-24 横浜ゴム株式会社 Rubber composition and pneumatic tire using the same
CN114341424A (en) * 2019-07-03 2022-04-12 北京化工大学 Composition for fiber surface treatment and fiber treatment method

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013147561A (en) * 2012-01-19 2013-08-01 Yokohama Rubber Co Ltd:The Rubber composition for tire and pneumatic tire using the same
CN105175783A (en) * 2015-10-10 2015-12-23 青岛科技大学 Surface treatment method for continuous basalt fiber framework material
CN106117670A (en) * 2016-07-06 2016-11-16 无锡宝通科技股份有限公司 A kind of resistance to calcination anti tear conveyer belt coating rubber and preparation method thereof
CN107352218A (en) * 2017-06-02 2017-11-17 浙江龙圣华橡胶有限公司 A kind of preparation method of basalt fibre canvas core conveyor belt
JP2019182920A (en) * 2018-04-03 2019-10-24 横浜ゴム株式会社 Rubber composition and pneumatic tire using the same
CN109486143A (en) * 2018-10-29 2019-03-19 安徽汇创新材料有限公司 A kind of septic tank heat resistant glass Steel material
CN114341424A (en) * 2019-07-03 2022-04-12 北京化工大学 Composition for fiber surface treatment and fiber treatment method

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
宋位华;孙云波;鲁学峰;盛翔;郝智;: "芳纶纤维表面处理及其增强天然橡胶复合材料的研究", 化工新型材料, no. 11 *

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