CN115558179A - High-strength flame-retardant modified composite rubber - Google Patents
High-strength flame-retardant modified composite rubber Download PDFInfo
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- CN115558179A CN115558179A CN202211266408.4A CN202211266408A CN115558179A CN 115558179 A CN115558179 A CN 115558179A CN 202211266408 A CN202211266408 A CN 202211266408A CN 115558179 A CN115558179 A CN 115558179A
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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
- C08L13/00—Compositions of rubbers containing carboxyl groups
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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
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
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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
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Abstract
The invention discloses a high-strength flame-retardant modified composite rubber which comprises the following raw materials in parts by weight: 70-100 parts of carboxyl nitrile rubber; 24-45 parts of ethylene propylene diene monomer; 18-36 parts of chloroprene rubber; 3-12 parts of dicumyl peroxide; 13-28 parts of a flame-retardant reinforcing multi-effect auxiliary agent; 5-14 parts of carbon black; 1-3.5 parts by weight of sulfur; 2-5 parts of zinc oxide; 2-6 parts of stearic acid; 1-3.5 parts of an accelerator; 1.2-4 parts of anti-aging agent; 0.5-3.8 parts of coupling agent. The composite rubber with excellent strength and flame retardant property is prepared by the enhancing and modifying effects of the flame-retardant reinforcing multi-effect auxiliary agent, and has a good application prospect.
Description
Technical Field
The invention relates to the field of rubber materials, in particular to high-strength flame-retardant modified composite rubber.
Background
The rubber material is widely applied to various production fields, and in some application scenes, such as electric wires, cables, electronic devices and the like, higher requirements are provided for the strength and the flame retardant property of rubber, and the traditional rubber is modified by adding other raw materials to improve the strength and the flame retardant property. For example, patent CN104311931B discloses a high-strength, aging-resistant, abrasion-resistant, flame-retardant compounded rubber, which is added with inorganic flame retardant antimony trioxide to impart flame-retardant performance, and added with modified titanium dioxide, hard china clay, reinforcing carbon black, kaolin, and barite powder as reinforcing fillers to improve the strength. However, antimony trioxide, an inorganic flame retardant, has a defect of poor compatibility with a rubber system and easily migrates to the surface of the rubber system to cause failure, and the inorganic reinforcing filler has a defect of difficulty in sufficiently dispersing in an organic rubber system, so that it is difficult for these modifiers to actually exert their effects sufficiently.
Therefore, there is a need for improvements in the prior art to provide a more reliable solution.
Disclosure of Invention
The invention aims to solve the technical problem of providing a high-strength flame-retardant modified composite rubber aiming at the defects in the prior art.
In order to solve the technical problems, the invention adopts the technical scheme that: a high-strength flame-retardant modified composite rubber comprises the following raw materials in parts by weight:
preferably, the flame-retardant reinforcing multi-effect auxiliary agent is prepared by the following method:
s1, preparing porous silicon dioxide microspheres;
s2, loading an inorganic flame retardant on the porous silicon dioxide microspheres to obtain loaded microspheres;
s3, carrying out surface modification on the loaded microspheres;
s4, coating a hole sealing film on the loaded microspheres to obtain functional microspheres;
s5, grafting the functional microspheres to graphene oxide to obtain the flame-retardant reinforcing multi-effect auxiliary agent.
Preferably, the step S1 specifically includes:
s1-1, adding 4-12g of hexadecyl trimethyl ammonium bromide into 80-200g of ethanol water solution, then adding 1-5g of ammonia water, and uniformly stirring;
s1-2, dropwise adding 4-8g of tetraethoxysilane under continuous stirring, continuously stirring for 3-6h, carrying out centrifugal filtration, and drying a solid product at 70-95 ℃ for 1-4h;
s1-3, and finally calcining for 6-10h at 580-700 ℃ to obtain the porous silica microspheres.
Preferably, the step S2 specifically includes:
s2-1, adding magnesium sulfate into deionized water, stirring, adding the porous silicon dioxide microspheres prepared in the step S1, and carrying out ultrasonic treatment for 30-60min to obtain a precursor solution; wherein the mass ratio of the magnesium sulfate to the porous silica microspheres is 4;
s2-2, dropwise adding ammonia water into the precursor liquid under continuous stirring until the precipitate is not increased any more, stopping dropwise adding, filtering, washing a solid product, and drying to obtain the load microsphere.
Preferably, the step S3 specifically includes:
s3-1, adding the loaded microspheres into an ethanol water solution, adding 3- (trimethoxysilyl) propyl-2-methyl-2-acrylate, and stirring for 10-45min;
s3-2, dropwise adding ammonia water under the protection of nitrogen, stirring for 6-12h at 45-65 ℃, centrifuging, washing a solid product with ethanol, and drying at 50-70 ℃ to obtain surface modified load microspheres;
wherein the supported microsphere is: the mass ratio of the 3- (trimethoxysilyl) propyl-2-methyl-2-acrylate is 8.
Preferably, the step S4 specifically includes:
s4-1, adding the surface-modified load microspheres, cerium acetate and PVP into an ethanol aqueous solution, and carrying out ultrasonic oscillation for 15-45min;
s4-2, adding styrene and AIBN, protecting with nitrogen, stirring for 6-15h at 60-90 ℃, centrifuging, washing a solid product with ethanol, and drying in vacuum at 60-90 ℃ to obtain the functional microspheres;
wherein, the surface modification load microsphere: the mass ratio of the cerium acetate is 100: the mass ratio of styrene is 1.
Preferably, the step S5 specifically includes:
s5-1, adding graphene oxide into ethanol, and carrying out ultrasonic treatment for 30-90min to obtain a graphene oxide dispersion liquid;
s5-2, adding the functional microspheres into an ethanol water solution, and carrying out ultrasonic treatment for 15-45min to obtain a microsphere dispersion liquid;
s5-3, mixing the graphene oxide dispersion liquid and the microsphere dispersion liquid, stirring and reacting at 65-80 ℃ for 6-14h, performing suction filtration after the reaction is finished, washing a solid product with ethanol, and performing vacuum drying at 55-75 ℃ to obtain the flame-retardant reinforcing multi-effect auxiliary agent;
wherein the mass ratio of the graphene oxide to the functional microspheres is 0.2-0.8.
Preferably, the high-strength flame-retardant modified composite rubber comprises the following raw materials in parts by weight:
preferably, the coupling agent is one or a mixture of more of a silane coupling agent KH-560, a silane coupling agent KH-570, a silane coupling agent A-172 and a silane coupling agent A-171, the anti-aging agent is one or a mixture of more of an anti-aging agent 4020, an anti-aging agent MC, an anti-aging agent RD and an anti-aging agent SP, and the accelerator is one or a mixture of more of an accelerator EZ, an accelerator MZ, an accelerator M, an accelerator DM and an accelerator PZ.
Preferably, the preparation method of the high-strength flame-retardant modified composite rubber comprises the following steps:
1) Adding carboxyl nitrile rubber, ethylene propylene diene monomer and chloroprene rubber into an open mill, and plasticating for 3-10min at 65-85 ℃ and 180-250 rpm;
2) Then adding the composite reinforcing agent, carbon black, zinc oxide, stearic acid, an anti-aging agent and a coupling agent, and plasticating for 2-8min at 70-98 ℃ and 120-160 rpm;
3) Adding dicumyl peroxide, sulfur and accelerator, and plasticating at 75-90 deg.C and 110-155rpm for 4-15min; finally, triangular packaging, rolling, thinly passing and then discharging the rubber sheets to obtain rubber compound;
4) And vulcanizing the rubber compound at 145-170 ℃ and 10-20MPa for 20-45min to obtain the high-strength flame-retardant modified composite rubber.
The beneficial effects of the invention are:
according to the invention, the composite rubber with excellent strength and flame retardant property is prepared by the enhancing and modifying effects of the flame retardant and reinforcing multi-effect auxiliary agent, and the composite rubber has a good application prospect;
according to the invention, a flame-retardant reinforcing multi-effect auxiliary agent is obtained by constructing a graphene oxide composite system grafted with functional microspheres, and can be fully dispersed in a rubber material system, so that the modification reinforcing effect of each functional component is effectively exerted, and the effects of improving the strength and the flame-retardant property of the composite rubber material can be simultaneously achieved;
according to the invention, porous silica microspheres with rich void structures are prepared, and then a large amount of magnesium hydroxide inorganic flame retardant is loaded on the porous silica microspheres through in-situ precipitation to obtain loaded microspheres; then, carrying out surface modification on the loaded microsphere by using a coupling agent 3- (trimethoxysilyl) propyl-2-methyl-2-acrylate, so that a double-bond functional group capable of participating in styrene polymerization reaction is grafted on the surface of the loaded microsphere; then coating a polystyrene film on the loaded microspheres by using a dispersion polymerization method, and in the step, adding cerium acetate to connect cerium ions on the loaded microspheres and further doping the cerium ions into a film structure; and finally, connecting the functional microspheres to the surface of the graphene oxide with a two-dimensional structure through the anchoring effect of cerium ions to construct the flame-retardant reinforcing multi-effect auxiliary agent.
In the flame-retardant reinforcing multi-effect auxiliary agent structure system constructed by the invention, the reinforcing flame-retardant effect of graphene oxide and the excellent flame-retardant property of magnesium hydroxide can be fully utilized, the interaction force between the graphene oxide and a rubber interface can be enhanced, the defects that the graphene oxide and magnesium hydroxide flame retardant are difficult to disperse in a rubber system, the magnesium hydroxide is easy to migrate on the surface, is easy to decompose and lose efficacy and the like are overcome, and the strength and the flame-retardant property of rubber can be remarkably improved.
Detailed Description
The present invention is further described in detail below with reference to examples so that those skilled in the art can practice the invention with reference to the description.
It will be understood that terms such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
The test methods used in the following examples are all conventional methods unless otherwise specified. The material reagents and the like used in the following examples are commercially available unless otherwise specified. The following examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The invention provides a high-strength flame-retardant modified composite rubber which comprises the following raw materials in parts by weight:
in a preferred embodiment, the coupling agent is one or a mixture of more of a silane coupling agent KH-560, a silane coupling agent KH-570, a silane coupling agent A-172 and a silane coupling agent A-171, the anti-aging agent is one or a mixture of more of an anti-aging agent 4020, an anti-aging agent MC, an anti-aging agent RD and an anti-aging agent SP, and the accelerator is one or a mixture of more of a promoter EZ, a promoter MZ, a promoter M, a promoter DM and a promoter PZ.
In a preferred embodiment, the preparation method of the high-strength flame-retardant modified composite rubber comprises the following steps:
1) Adding carboxyl nitrile rubber, ethylene propylene diene monomer rubber and chloroprene rubber into an open mill, and plasticating for 3-10min at 65-85 ℃ and 180-250 rpm;
2) Then adding the composite reinforcing agent, carbon black, zinc oxide, stearic acid, an anti-aging agent and a coupling agent, and plasticating for 2-8min at 70-98 ℃ and 120-160 rpm;
3) Adding dicumyl peroxide, sulfur and accelerator, and plasticating at 75-90 deg.C and 110-155rpm for 4-15min; finally, triangular packaging, rolling, thinly passing and then discharging the rubber sheets to obtain rubber compound;
4) And vulcanizing the mixed rubber at 145-170 ℃ and 10-20MPa for 20-45min to obtain the high-strength flame-retardant modified composite rubber.
In a preferred embodiment, the flame-retardant reinforcing multi-effect auxiliary agent is prepared by the following method:
s1, preparing porous silicon dioxide microspheres
S1-1, adding 4-12g of hexadecyl trimethyl ammonium bromide into 80-200g of ethanol water solution, then adding 1-5g of ammonia water, and uniformly stirring;
s1-2, dropwise adding 4-8g of tetraethoxysilane under continuous stirring, continuously stirring for 3-6h, carrying out centrifugal filtration, and drying a solid product at 70-95 ℃ for 1-4h;
s1-3, and finally calcining for 6-10h at 580-700 ℃ to obtain the porous silica microspheres.
S2, preparing the loaded microspheres
S2-1, adding magnesium sulfate into deionized water, stirring, adding the porous silicon dioxide microspheres prepared in the step S1, and carrying out ultrasonic treatment for 30-60min to obtain a precursor solution; wherein the mass ratio of the magnesium sulfate to the porous silica microspheres is 4;
and S2-2, dropwise adding ammonia water into the forward-flooding liquid under continuous stirring until the precipitate is not increased any more, stopping dropwise adding, filtering, washing a solid product, and drying to obtain the load microsphere.
S3, carrying out surface modification on the loaded microspheres
S3-1, adding the loaded microspheres into an ethanol water solution, adding 3- (trimethoxysilyl) propyl-2-methyl-2-acrylate, and stirring for 10-45min;
s3-2, dropwise adding ammonia water under the protection of nitrogen, stirring for 6-12h at 45-65 ℃, centrifuging, washing a solid product with ethanol, and drying at 50-70 ℃ to obtain surface modified load microspheres;
wherein, the loading microsphere: the mass ratio of the 3- (trimethoxysilyl) propyl-2-methyl-2-acrylate is 8.
S4, preparing functional microspheres
S4-1, adding the surface-modified load microspheres, cerium acetate and PVP into an ethanol aqueous solution, and carrying out ultrasonic oscillation for 15-45min;
s4-2, adding styrene and AIBN, stirring for 6-15h at 60-90 ℃ under the protection of nitrogen, centrifuging, washing a solid product with ethanol, and performing vacuum drying at 60-90 ℃ to obtain functional microspheres;
wherein, the surface modified load microsphere: the mass ratio of the cerium acetate is 100, and the mass ratio of the surface modified load microsphere is 0.2-5.5: the mass ratio of styrene is 1.
S5, grafting the functional microspheres to graphene oxide
S5-1, adding graphene oxide into ethanol, and carrying out ultrasonic treatment for 30-90min to obtain a graphene oxide dispersion liquid;
s5-2, adding the functional microspheres into an ethanol water solution, and carrying out ultrasonic treatment for 15-45min to obtain a microsphere dispersion liquid;
s5-3, mixing the graphene oxide dispersion liquid and the microsphere dispersion liquid, stirring and reacting at 65-80 ℃ for 6-14h, filtering after the reaction is finished, washing a solid product with ethanol, and drying in vacuum at 55-75 ℃ to obtain the flame-retardant reinforcing multi-effect assistant;
wherein the mass ratio of the graphene oxide to the functional microspheres is 0.2-0.8.
In the invention, the carboxyl is introduced into the carboxyl nitrile rubber to increase the polarity, so that the carboxyl nitrile rubber has the characteristics of high strength, aging resistance and the like, and the heat resistance, flame retardance and acid-base corrosion resistance of the rubber can be further improved by compounding the ethylene propylene diene monomer, the chloroprene rubber and the carboxyl nitrile rubber.
According to the invention, the flame-retardant reinforcing multi-effect auxiliary agent can simultaneously play a role in improving the strength and the flame-retardant performance of the composite rubber material, and can be fully dispersed into a rubber material system by constructing a graphene oxide composite system grafted with functional microspheres, so that the modification reinforcing effect of each functional component is effectively exerted, and the flame-retardant reinforcing multi-effect auxiliary agent is characterized in that: the preparation method comprises the steps of firstly preparing porous silica microspheres with rich void structures, and then loading a large amount of magnesium hydroxide inorganic flame retardant on the porous silica microspheres through in-situ precipitation to obtain loaded microspheres; then, carrying out surface modification on the loaded microsphere by using a coupling agent 3- (trimethoxysilyl) propyl-2-methyl-2-acrylate, so that a double-bond functional group capable of participating in styrene polymerization reaction is grafted on the surface of the loaded microsphere; then coating a polystyrene film on the loaded microspheres by using a dispersion polymerization method, and in the step, adding cerium acetate to connect cerium ions on the loaded microspheres and further doping the cerium ions into a film structure; and finally, connecting the functional microspheres to the surface of the graphene oxide with the two-dimensional structure through the anchor point effect of cerium ions.
The inorganic flame retardant magnesium hydroxide can realize effective flame retardance by means of mechanisms such as chemical decomposition, heat absorption, water release and the like when being heated, but the inorganic flame retardant magnesium hydroxide has the defects of difficult dispersion, easy surface migration, easy decomposition, failure and the like in an organic system, and can reduce the strength of the organic system when the addition amount is large due to difficult dispersion. According to the invention, the silica microspheres with porous structures are loaded with magnesium hydroxide, so that the defect of easy decomposition of the silica microspheres can be overcome, and further, the polystyrene coating sealing holes are used for realizing long-acting flame retardance of the magnesium hydroxide (when the polystyrene coating sealing holes are normally used, the magnesium hydroxide is sealed in the void structures of the silica microspheres and isolated from a rubber system, so that the strength of the rubber system is not influenced, the flame retardant efficiency can be kept for a long time, when the polystyrene film is heated to decompose and break, and the magnesium hydroxide overflows, so that the flame retardant effect can be effectively exerted), and the polystyrene can be used for remarkably improving the dispersibility of the silica microspheres in an organism system, so that the silica microspheres loaded with the magnesium hydroxide can be uniformly dispersed in a matrix rubber system, and the defects of difficult dispersion and easy surface migration of the magnesium hydroxide are overcome.
The silica microspheres are used as carriers of flame retardants, have certain flame retardant performance, and can improve the strength of rubber by virtue of the high strength and corrosion resistance of the microspheres.
When polystyrene coating is carried out, cerium ions added in the system can be connected to the microspheres through coordination with functional groups such as silicon hydroxyl groups on the surfaces of the silicon dioxide microspheres, rare earth cerium has high chemical activity and can provide large and multiple coordination bonds, and can form a multi-coordination complex with oxygen-containing functional groups such as hydroxyl groups and carboxyl groups, wherein the complex is used as an anchor point and is coordinated with the functional groups such as the silicon hydroxyl groups of the silicon dioxide microspheres and the carboxyl groups on the surfaces of graphene oxide, so that the effect of bridging the silicon dioxide microspheres and the graphene oxide is achieved; in addition, the rare earth cerium can also play a role in promoting the polymerization of styrene, and can form an active center to promote the polymerization reaction, thereby being beneficial to forming a complete polystyrene coating film with a smooth surface.
The polystyrene coating film can obviously improve the uniform dispersion performance of the silicon dioxide microspheres in a rubber system while realizing the hole sealing effect.
After the polystyrene-coated silica microspheres are grafted to the graphene oxide, the compatibility of the polystyrene to the silica microspheres and rubber is improved, so that the graphene oxide and the polystyrene-coated silica microspheres can be fully dispersed in a rubber system, and the problem that the graphene oxide is easy to agglomerate is solved; after the flame-retardant reinforcing multi-effect auxiliary agent is added into a rubber system, graphene oxide with a two-dimensional structure forms a network structure in the rubber system, and the polystyrene-coated silica microspheres can be used as a network center point, so that the strength of the network structure can be improved, and the reinforcing effect of the graphene oxide on the strength of the rubber can be improved; meanwhile, rare earth cerium in the flame-retardant reinforcing multi-effect auxiliary structural system can also form a coordination bond with a carboxyl functional group in the carboxyl nitrile rubber, so that the interface connection strength between the flame-retardant reinforcing multi-effect auxiliary system and a rubber system is further improved, and the integral strength of the rubber is improved.
Wherein, the graphene oxide can also play supplementary flame retardant efficiency when promoting intensity, and its fire-retardant principle is: (1) The graphene has a special two-dimensional layered structure, can promote the generation of carbon residues in the combustion process, and the carbon residues can be used as a physical barrier to prevent heat transfer and delay the escape of pyrolysis products (generally combustible substances) from a matrix; (2) The graphene has a large specific surface area, can effectively adsorb inflammable pyrolysis products, and provides a carbonization platform; (3) Graphene contains a large number of functional groups (carboxyl, hydroxyl, etc.) on the surface thereof, and the oxygen-containing functional groups decompose and dehydrate at high temperatures, absorb ambient thermal energy, and dilute ambient oxygen concentration, thereby suppressing combustion.
According to the invention, by constructing a special flame-retardant reinforcing multi-effect auxiliary agent structure system, the reinforcing flame-retardant effect of graphene oxide and the excellent flame-retardant property of magnesium hydroxide can be fully utilized, the interaction force between the graphene oxide and a rubber interface can be enhanced, the defects that the graphene oxide and magnesium hydroxide flame retardant are difficult to disperse in a rubber system, the magnesium hydroxide is easy to migrate on the surface, is easy to decompose and lose efficacy and the like are overcome, and the strength and the flame-retardant property of rubber can be remarkably improved.
Example 1
A high-strength flame-retardant modified composite rubber comprises the following raw materials in parts by weight:
wherein the coupling agent is a silane coupling agent A-172, the anti-aging agent is a mixture of an anti-aging agent MC and an anti-aging agent RD, and the accelerator is a mixture of an accelerator MZ and an accelerator PZ.
The preparation method of the high-strength flame-retardant modified composite rubber comprises the following steps:
1) Adding carboxyl nitrile rubber, ethylene propylene diene monomer and chloroprene rubber into an open mill, and plastifying at 70 ℃ and 220rpm for 5min;
2) Adding composite reinforcing agent, carbon black, zinc oxide, stearic acid, anti-aging agent and coupling agent, and plasticating for 4min at 85 ℃ and 140 rpm;
3) Adding dicumyl peroxide, sulfur and accelerator, and plastifying at 80 deg.C and 135rpm for 7min; finally, triangular packaging, rolling, thinning and discharging to obtain rubber compound;
4) And vulcanizing the rubber compound at 160 ℃ and 14MPa for 35min to obtain the high-strength flame-retardant modified composite rubber.
The flame-retardant reinforcing multi-effect auxiliary agent is prepared by the following method:
s1, preparing porous silicon dioxide microspheres
S1-1, adding 5g of hexadecyl trimethyl ammonium bromide into 100g of ethanol aqueous solution (the volume ratio of ethanol to water is 1;
s1-2, dropwise adding 6.4g of ethyl orthosilicate under continuous stirring, continuously stirring for 4 hours, carrying out centrifugal filtration, and drying a solid product at 75 ℃ for 2 hours;
s1-3, and finally calcining for 8 hours at 640 ℃ to obtain the porous silicon dioxide microspheres.
S2, preparing the load microsphere
S2-1, adding magnesium sulfate into deionized water, stirring, adding the porous silicon dioxide microspheres prepared in the step S1, and carrying out ultrasonic treatment for 40min to obtain a precursor solution; wherein the mass ratio of the magnesium sulfate to the porous silica microspheres is 2.5;
and S2-2, dropwise adding ammonia water with the concentration of 0.5mol/L into the forward flooding liquid under continuous stirring until no precipitate is increased, stopping dropwise adding, filtering, washing a solid product, and drying at 75 ℃ for 4 hours to obtain the load microsphere.
S3, carrying out surface modification on the loaded microspheres
S3-1, adding the loaded microspheres into an ethanol water solution (the volume ratio of ethanol to water is 1;
s3-2, dropwise adding ammonia water with the concentration of 0.5mol/L under the protection of nitrogen, stirring for 8 hours at 50 ℃, centrifuging, washing a solid product with ethanol, and drying at 65 ℃ to obtain surface-modified load microspheres;
wherein, the loading of the microspheres: the mass ratio of the 3- (trimethoxysilyl) propyl-2-methyl-2-acrylate is 12; ammonia water: the mass ratio of 3- (trimethoxysilyl) propyl-2-methyl-2-acrylate was 4.
S4, preparing functional microspheres
S4-1, adding the surface-modified load microspheres, cerium acetate and PVP (polyvinylpyrrolidone) into an ethanol water solution (the volume ratio of ethanol to water is 3: 1), and performing ultrasonic oscillation for 30min;
s4-2, adding styrene and AIBN (azodiisobutyronitrile), stirring for 12 hours at 75 ℃ under the protection of nitrogen, centrifuging, washing a solid product with ethanol, and drying in vacuum at 60 ℃ to obtain functional microspheres;
wherein, the surface modification load microsphere: the mass ratio of the cerium acetate is 100: the mass ratio of styrene is 1.
S5, grafting the functional microspheres to graphene oxide
S5-1, adding graphene oxide (purchased from Jiangsu Xiancheng nano material science and technology limited, the same shall apply hereinafter) into ethanol, and carrying out ultrasonic treatment for 60min to obtain a graphene oxide dispersion liquid;
s5-2, adding the functional microspheres into an ethanol water solution (the volume ratio of ethanol to water is 1;
s5-3, mixing the graphene oxide dispersion liquid and the microsphere dispersion liquid, stirring at 70 ℃ for reaction for 12 hours, carrying out suction filtration after the reaction is finished, washing a solid product with ethanol, and carrying out vacuum drying at 60 ℃ to obtain the flame-retardant reinforcing multi-effect auxiliary agent;
wherein the mass ratio of the graphene oxide to the functional microspheres is 0.4.
Example 2
A high-strength flame-retardant modified composite rubber comprises the following raw materials in parts by weight:
wherein the coupling agent is a silane coupling agent A-172, the anti-aging agent is a mixture of an anti-aging agent MC and an anti-aging agent RD, and the accelerator is a mixture of an accelerator MZ and an accelerator PZ.
The preparation method of the high-strength flame-retardant modified composite rubber comprises the following steps:
1) Adding carboxyl nitrile rubber, ethylene propylene diene monomer rubber and chloroprene rubber into an open mill, and plasticating for 5min at 70 ℃ and 220 rpm;
2) Adding composite reinforcing agent, carbon black, zinc oxide, stearic acid, anti-aging agent and coupling agent, and plasticating for 4min at 85 ℃ and 140 rpm;
3) Adding dicumyl peroxide, sulfur and accelerator, and plasticating for 7min at 80 ℃ and 135 rpm; finally, triangular packaging, rolling, thinning and discharging to obtain rubber compound;
4) And vulcanizing the rubber compound at 160 ℃ and 14MPa for 35min to obtain the high-strength flame-retardant modified composite rubber.
The flame-retardant reinforcing multi-effect auxiliary agent is prepared by the following method:
s1, preparing porous silicon dioxide microspheres
S1-1, adding 5g of hexadecyl trimethyl ammonium bromide into 100g of ethanol aqueous solution (the volume ratio of ethanol to water is 1;
s1-2, dropwise adding 6.4g of tetraethoxysilane under continuous stirring, continuously stirring for 4 hours, carrying out centrifugal filtration, and drying a solid product at the temperature of 75 ℃ for 2 hours;
s1-3, and finally calcining for 8 hours at 640 ℃ to obtain the porous silicon dioxide microspheres.
S2, preparing the loaded microspheres
S2-1, adding magnesium sulfate into deionized water, stirring, adding the porous silicon dioxide microspheres prepared in the step S1, and performing ultrasonic treatment for 40min to obtain a precursor solution; wherein the mass ratio of the magnesium sulfate to the porous silica microspheres is 2.5;
and S2-2, dropwise adding ammonia water with the concentration of 0.5mol/L into the forward flooding liquid under continuous stirring until no precipitate is increased, stopping dropwise adding, filtering, washing a solid product, and drying at 75 ℃ for 4 hours to obtain the load microsphere.
S3, carrying out surface modification on the loaded microspheres
S3-1, adding the loaded microspheres into an ethanol water solution (the volume ratio of ethanol to water is 1;
s3-2, dropwise adding ammonia water with the concentration of 0.5mol/L under the protection of nitrogen, stirring for 8 hours at 50 ℃, centrifuging, washing a solid product with ethanol, and drying at 65 ℃ to obtain a surface modified load microsphere;
wherein, the loading microsphere: the mass ratio of the 3- (trimethoxysilyl) propyl-2-methyl-2-acrylate is 12; ammonia water: the mass ratio of 3- (trimethoxysilyl) propyl-2-methyl-2-acrylate was 4.
S4, preparing functional microspheres
S4-1, adding the surface-modified load microspheres, cerium acetate and PVP (polyvinylpyrrolidone) into an ethanol water solution (the volume ratio of ethanol to water is 3;
s4-2, adding styrene and AIBN (azodiisobutyronitrile), stirring for 12 hours at 75 ℃ under the protection of nitrogen, centrifuging, washing a solid product with ethanol, and drying in vacuum at 60 ℃ to obtain functional microspheres;
wherein, the surface modification load microsphere: the mass ratio of the cerium acetate is 100: the mass ratio of styrene is 1.
S5, grafting the functional microspheres to graphene oxide
S5-1, adding graphene oxide into ethanol, and performing ultrasonic treatment for 60min to obtain a graphene oxide dispersion liquid;
s5-2, adding the functional microspheres into an ethanol water solution (the volume ratio of ethanol to water is 1;
s5-3, mixing the graphene oxide dispersion liquid and the microsphere dispersion liquid, stirring at 70 ℃ for reaction for 12 hours, carrying out suction filtration after the reaction is finished, washing a solid product with ethanol, and carrying out vacuum drying at 60 ℃ to obtain the flame-retardant reinforcing multi-effect assistant;
wherein the mass ratio of the graphene oxide to the functional microspheres is 0.4.
Example 3
A high-strength flame-retardant modified composite rubber comprises the following raw materials in parts by weight:
wherein the coupling agent is a silane coupling agent A-172, the anti-aging agent is a mixture of an anti-aging agent MC and an anti-aging agent RD, and the accelerator is a mixture of an accelerator MZ and an accelerator PZ.
The preparation method of the high-strength flame-retardant modified composite rubber comprises the following steps:
1) Adding carboxyl nitrile rubber, ethylene propylene diene monomer and chloroprene rubber into an open mill, and plastifying at 70 ℃ and 220rpm for 5min;
2) Adding composite reinforcing agent, carbon black, zinc oxide, stearic acid, anti-aging agent and coupling agent, and plasticating for 4min at 85 ℃ and 140 rpm;
3) Adding dicumyl peroxide, sulfur and accelerator, and plastifying at 80 deg.C and 135rpm for 7min; finally, triangular packaging, rolling, thinly passing and then discharging the rubber sheets to obtain rubber compound;
4) And vulcanizing the rubber compound at 160 ℃ and 14MPa for 35min to obtain the high-strength flame-retardant modified composite rubber.
The flame-retardant reinforcing multi-effect auxiliary agent is prepared by the following method:
s1, preparing porous silicon dioxide microspheres
S1-1, adding 5g of hexadecyl trimethyl ammonium bromide into 100g of ethanol aqueous solution (the volume ratio of ethanol to water is 1;
s1-2, dropwise adding 6.4g of ethyl orthosilicate under continuous stirring, continuously stirring for 4 hours, carrying out centrifugal filtration, and drying a solid product at 75 ℃ for 2 hours;
s1-3, and finally calcining for 8 hours at 640 ℃ to obtain the porous silicon dioxide microspheres.
S2, preparing the loaded microspheres
S2-1, adding magnesium sulfate into deionized water, stirring, adding the porous silicon dioxide microspheres prepared in the step S1, and performing ultrasonic treatment for 40min to obtain a precursor solution; wherein the mass ratio of the magnesium sulfate to the porous silica microspheres is 2.5;
and S2-2, dropwise adding ammonia water with the concentration of 0.5mol/L into the forward flooding liquid under continuous stirring until no precipitate is increased, stopping dropwise adding, filtering, washing a solid product, and drying at 75 ℃ for 4 hours to obtain the load microsphere.
S3, carrying out surface modification on the loaded microspheres
S3-1, adding the loaded microspheres into an ethanol water solution (the volume ratio of ethanol to water is 1;
s3-2, dropwise adding ammonia water with the concentration of 0.5mol/L under the protection of nitrogen, stirring for 8 hours at 50 ℃, centrifuging, washing a solid product with ethanol, and drying at 65 ℃ to obtain surface-modified load microspheres;
wherein, the loading of the microspheres: the mass ratio of the 3- (trimethoxysilyl) propyl-2-methyl-2-acrylate is 12; ammonia water: the mass ratio of 3- (trimethoxysilyl) propyl-2-methyl-2-acrylate was 4.
S4, preparing functional microspheres
S4-1, adding the surface-modified load microspheres, cerium acetate and PVP (polyvinylpyrrolidone) into an ethanol water solution (the volume ratio of ethanol to water is 3: 1), and performing ultrasonic oscillation for 30min;
s4-2, adding styrene and AIBN (azodiisobutyronitrile), stirring for 12 hours at 75 ℃ under the protection of nitrogen, centrifuging, washing a solid product with ethanol, and drying in vacuum at 60 ℃ to obtain functional microspheres;
wherein, the surface modification load microsphere: the mass ratio of the cerium acetate is 100: the mass ratio of styrene is 1.
S5, grafting the functional microspheres to graphene oxide
S5-1, adding graphene oxide into ethanol, and performing ultrasonic treatment for 60min to obtain a graphene oxide dispersion liquid;
s5-2, adding the functional microspheres into an ethanol water solution (the volume ratio of ethanol to water is 1;
s5-3, mixing the graphene oxide dispersion liquid and the microsphere dispersion liquid, stirring at 70 ℃ for reaction for 12 hours, carrying out suction filtration after the reaction is finished, washing a solid product with ethanol, and carrying out vacuum drying at 60 ℃ to obtain the flame-retardant reinforcing multi-effect auxiliary agent;
wherein the mass ratio of the graphene oxide to the functional microspheres is 0.4.
Example 4
A high-strength flame-retardant modified composite rubber comprises the following raw materials in parts by weight:
wherein the coupling agent is a silane coupling agent A-172, the anti-aging agent is a mixture of an anti-aging agent MC and an anti-aging agent RD, and the accelerator is a mixture of an accelerator MZ and an accelerator PZ.
The preparation method of the high-strength flame-retardant modified composite rubber comprises the following steps:
1) Adding carboxyl nitrile rubber, ethylene propylene diene monomer and chloroprene rubber into an open mill, and plastifying at 70 ℃ and 220rpm for 5min;
2) Then adding the composite reinforcing agent, carbon black, zinc oxide, stearic acid, an anti-aging agent and a coupling agent, and plasticating for 4min at 85 ℃ and 140 rpm;
3) Adding dicumyl peroxide, sulfur and accelerator, and plastifying at 80 deg.C and 135rpm for 7min; finally, triangular packaging, rolling, thinly passing and then discharging the rubber sheets to obtain rubber compound;
4) And vulcanizing the rubber compound for 35min at 160 ℃ and 14MPa to obtain the high-strength flame-retardant modified composite rubber.
The flame-retardant reinforcing multi-effect auxiliary agent is prepared by the following method:
s1, preparing porous silicon dioxide microspheres
S1-1, adding 5g of hexadecyl trimethyl ammonium bromide into 100g of ethanol aqueous solution (the volume ratio of ethanol to water is 1;
s1-2, dropwise adding 6.4g of ethyl orthosilicate under continuous stirring, continuously stirring for 4 hours, carrying out centrifugal filtration, and drying a solid product at 75 ℃ for 2 hours;
s1-3, and finally calcining for 8 hours at 640 ℃ to obtain the porous silicon dioxide microspheres.
S2, preparing the loaded microspheres
S2-1, adding magnesium sulfate into deionized water, stirring, adding the porous silicon dioxide microspheres prepared in the step S1, and performing ultrasonic treatment for 40min to obtain a precursor solution; wherein the mass ratio of the magnesium sulfate to the porous silica microspheres is 2.5;
s2-2, dropwise adding 0.5mol/L ammonia water into the forward-driving liquid under continuous stirring until no precipitate is increased, filtering, washing a solid product, and drying at 75 ℃ for 4 hours to obtain the load microsphere.
S3, carrying out surface modification on the loaded microspheres
S3-1, adding the loaded microspheres into an ethanol water solution (the volume ratio of ethanol to water is 1;
s3-2, dropwise adding ammonia water with the concentration of 0.5mol/L under the protection of nitrogen, stirring for 8 hours at 50 ℃, centrifuging, washing a solid product with ethanol, and drying at 65 ℃ to obtain surface-modified load microspheres;
wherein, the loading microsphere: the mass ratio of the 3- (trimethoxysilyl) propyl-2-methyl-2-acrylate is 12; ammonia water: the mass ratio of 3- (trimethoxysilyl) propyl-2-methyl-2-acrylate was 4.
S4, preparing functional microspheres
S4-1, adding the surface-modified load microspheres, cerium acetate and PVP (polyvinylpyrrolidone) into an ethanol water solution (the volume ratio of ethanol to water is 3: 1), and performing ultrasonic oscillation for 30min;
s4-2, adding styrene and AIBN (azodiisobutyronitrile), stirring for 12 hours at 75 ℃ under the protection of nitrogen, centrifuging, washing a solid product with ethanol, and drying in vacuum at 60 ℃ to obtain functional microspheres;
wherein, the surface modification load microsphere: the mass ratio of the cerium acetate is 100: the mass ratio of styrene is 1.
S5, grafting the functional microspheres to graphene oxide
S5-1, adding graphene oxide into ethanol, and performing ultrasonic treatment for 60min to obtain a graphene oxide dispersion liquid;
s5-2, adding the functional microspheres into an ethanol water solution (the volume ratio of ethanol to water is 1;
s5-3, mixing the graphene oxide dispersion liquid and the microsphere dispersion liquid, stirring at 70 ℃ for reaction for 12 hours, carrying out suction filtration after the reaction is finished, washing a solid product with ethanol, and carrying out vacuum drying at 60 ℃ to obtain the flame-retardant reinforcing multi-effect assistant;
wherein the mass ratio of the graphene oxide to the functional microspheres is 0.4.
Comparative example 1
The rubber composition is basically the same as that in example 2, except that the composite rubber comprises the following raw materials in parts by weight:
comparative example 2
The rubber composition is basically the same as example 2, except that the compounded rubber comprises the following raw materials in parts by weight:
comparative example 3
The flame-retardant reinforcing multi-effect auxiliary agent in the embodiment is basically the same as the flame-retardant reinforcing multi-effect auxiliary agent in the embodiment 2, except that the flame-retardant reinforcing multi-effect auxiliary agent in the embodiment is prepared by the following method:
s1, preparing porous silicon dioxide microspheres
S1-1, adding 5g of hexadecyl trimethyl ammonium bromide into 100g of ethanol aqueous solution (the volume ratio of ethanol to water is 1;
s1-2, dropwise adding 6.4g of ethyl orthosilicate under continuous stirring, continuously stirring for 4 hours, carrying out centrifugal filtration, and drying a solid product at 75 ℃ for 2 hours;
s1-3, and finally calcining for 8 hours at 640 ℃ to obtain the porous silicon dioxide microspheres.
S2, preparing the load microsphere
S2-1, adding magnesium sulfate into deionized water, stirring, adding the porous silicon dioxide microspheres prepared in the step S1, and carrying out ultrasonic treatment for 40min to obtain a precursor solution; wherein the mass ratio of the magnesium sulfate to the porous silica microspheres is 2.5;
s2-2, dropwise adding 0.5mol/L ammonia water into the forward-driving liquid under continuous stirring until no precipitate is increased, filtering, washing a solid product, and drying at 75 ℃ for 4 hours to obtain the load microsphere.
S3, carrying out surface modification on the loaded microspheres
S3-1, adding the loaded microspheres into an ethanol water solution (the volume ratio of ethanol to water is 1;
s3-2, dropwise adding ammonia water with the concentration of 0.5mol/L under the protection of nitrogen, stirring for 8 hours at 50 ℃, centrifuging, washing a solid product with ethanol, and drying at 65 ℃ to obtain surface-modified load microspheres;
wherein, the loading of the microspheres: the mass ratio of the 3- (trimethoxysilyl) propyl-2-methyl-2-acrylate is 12; ammonia water: the mass ratio of 3- (trimethoxysilyl) propyl-2-methyl-2-acrylate was 4.
S4, preparing functional microspheres
S4-1, adding the surface-modified load microspheres and PVP (polyvinylpyrrolidone) into an ethanol water solution (the volume ratio of ethanol to water is 3;
s4-2, adding styrene and AIBN (azodiisobutyronitrile), stirring for 12 hours at 75 ℃ under the protection of nitrogen, centrifuging, washing a solid product with ethanol, and drying in vacuum at 60 ℃ to obtain functional microspheres;
wherein, the surface modified load microsphere: the mass ratio of styrene is 1.
S5, grafting the functional microspheres to graphene oxide
S5-1, adding graphene oxide into ethanol, and performing ultrasonic treatment for 60min to obtain a graphene oxide dispersion liquid;
s5-2, adding the functional microspheres into an ethanol water solution (the volume ratio of ethanol to water is 1;
s5-3, mixing the graphene oxide dispersion liquid and the microsphere dispersion liquid, stirring at 70 ℃ for reaction for 12 hours, carrying out suction filtration after the reaction is finished, washing a solid product with ethanol, and carrying out vacuum drying at 60 ℃ to obtain the flame-retardant reinforcing multi-effect auxiliary agent;
wherein the mass ratio of the graphene oxide to the functional microspheres is 0.4.
The compounded rubbers prepared in examples 1 to 4 and comparative examples 1 to 3 were subjected to the following performance tests, the test items including:
1. tensile properties were tested according to standard GB/T528-2009 (25 ℃);
2. the oxygen index test was carried out according to the standard GB/T10707-2008.
The test results are shown in table 1 below:
TABLE 1
| Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Tensile strength MPa | 26.4 | 27.6 | 28.1 | 27.9 | 18.2 | 20.1 | 20.4 |
| Elongation at break% | 535 | 541 | 539 | 544 | 369 | 417 | 482 |
| Oxygen index% | 42.5 | 44.1 | 45.0 | 44.7 | 21.3 | 26.4 | 39.5 |
Wherein, the higher the oxygen index of the material, the higher the oxygen concentration required for ignition, the less easily ignited, and the better the flame retardance.
As can be seen from the results of Table 1, the compounded rubbers prepared in examples 1 to 4 have excellent strength and flame retardant properties; in the comparative example 2, the defects that monomers such as graphite oxide, magnesium hydroxide and the like are difficult to disperse in a rubber system and the like cannot be overcome, and the strength and the flame retardant property are obviously reduced; in the comparative example 3, rare earth cerium with an anchor point effect is not introduced, and the interface connection acting force between the flame-retardant reinforcing multi-effect auxiliary agent system and the rubber system is weakened, so that the strength of the composite rubber is reduced.
While embodiments of the invention have been disclosed above, it is not limited to the applications listed in the description and the embodiments, which are fully applicable in all kinds of fields of application of the invention, and further modifications may readily be effected by those skilled in the art, so that the invention is not limited to the specific details without departing from the general concept defined by the claims and the scope of equivalents.
Claims (10)
1. The high-strength flame-retardant modified composite rubber is characterized by comprising the following raw materials in parts by weight:
2. the high-strength flame-retardant modified composite rubber according to claim 1, wherein the flame-retardant reinforcing multi-effect auxiliary is prepared by the following method:
s1, preparing porous silicon dioxide microspheres;
s2, loading an inorganic flame retardant on the porous silicon dioxide microspheres to obtain loaded microspheres;
s3, carrying out surface modification on the loaded microspheres;
s4, coating a hole sealing film on the loaded microspheres to obtain functional microspheres;
s5, grafting the functional microspheres to graphene oxide to obtain the flame-retardant reinforcing multi-effect auxiliary agent.
3. The high-strength flame-retardant modified compounded rubber according to claim 2, wherein the step S1 specifically comprises:
s1-1, adding 4-12g of hexadecyl trimethyl ammonium bromide into 80-200g of ethanol water solution, then adding 1-5g of ammonia water, and uniformly stirring;
s1-2, dropwise adding 4-8g of ethyl orthosilicate under continuous stirring, continuously stirring for 3-6h, carrying out centrifugal filtration, and drying a solid product at 70-95 ℃ for 1-4h;
s1-3, and finally calcining for 6-10h at 580-700 ℃ to obtain the porous silica microspheres.
4. The high-strength flame-retardant modified compounded rubber according to claim 3, wherein the step S2 specifically comprises:
s2-1, adding magnesium sulfate into deionized water, stirring, adding the porous silicon dioxide microspheres prepared in the step S1, and carrying out ultrasonic treatment for 30-60min to obtain a precursor solution; wherein the mass ratio of the magnesium sulfate to the porous silica microspheres is 4;
s2-2, dropwise adding ammonia water into the precursor liquid under continuous stirring until the precipitate is not increased any more, stopping dropwise adding, filtering, washing a solid product, and drying to obtain the load microsphere.
5. The high-strength flame-retardant modified compounded rubber according to claim 4, wherein the step S3 specifically comprises:
s3-1, adding the loaded microspheres into an ethanol water solution, adding 3- (trimethoxysilyl) propyl-2-methyl-2-acrylate, and stirring for 10-45min;
s3-2, dropwise adding ammonia water under the protection of nitrogen, stirring for 6-12h at 45-65 ℃, centrifuging, washing a solid product with ethanol, and drying at 50-70 ℃ to obtain surface modified load microspheres;
wherein the supported microsphere is: the mass ratio of the 3- (trimethoxysilyl) propyl-2-methyl-2-acrylate is 8.
6. The high-strength flame-retardant modified compounded rubber according to claim 5, wherein the step S4 specifically comprises:
s4-1, adding the surface-modified load microspheres, cerium acetate and PVP into an ethanol aqueous solution, and carrying out ultrasonic oscillation for 15-45min;
s4-2, adding styrene and AIBN, stirring for 6-15h at 60-90 ℃ under the protection of nitrogen, centrifuging, washing a solid product with ethanol, and performing vacuum drying at 60-90 ℃ to obtain the functional microspheres;
wherein, the surface modified load microsphere: the mass ratio of the cerium acetate is 100: the mass ratio of styrene is 1.
7. The high-strength flame-retardant modified compounded rubber according to claim 6, wherein the step S5 specifically comprises:
s5-1, adding graphene oxide into ethanol, and carrying out ultrasonic treatment for 30-90min to obtain a graphene oxide dispersion liquid;
s5-2, adding the functional microspheres into an ethanol water solution, and carrying out ultrasonic treatment for 15-45min to obtain a microsphere dispersion liquid;
s5-3, mixing the graphene oxide dispersion liquid and the microsphere dispersion liquid, stirring and reacting at 65-80 ℃ for 6-14h, filtering after the reaction is finished, washing a solid product with ethanol, and drying in vacuum at 55-75 ℃ to obtain the flame-retardant reinforcing multi-effect assistant;
wherein the mass ratio of the graphene oxide to the functional microspheres is 0.2-0.8.
8. The high-strength flame-retardant modified compounded rubber according to claim 7, characterized by comprising the following raw materials in parts by weight:
9. the high-strength flame-retardant modified compounded rubber according to claim 8, wherein the coupling agent is a mixture of one or more of silane coupling agent KH-560, silane coupling agent KH-570, silane coupling agent A-172 and silane coupling agent A-171, the antioxidant is a mixture of one or more of antioxidant 4020, antioxidant MC, antioxidant RD and antioxidant SP, and the accelerator is a mixture of one or more of accelerator EZ, accelerator MZ, accelerator M, accelerator DM and accelerator PZ.
10. The high-strength flame-retardant modified compounded rubber according to any one of claims 1 to 9, characterized in that the preparation method comprises the following steps:
1) Adding carboxyl nitrile rubber, ethylene propylene diene monomer rubber and chloroprene rubber into an open mill, and plasticating for 3-10min at 65-85 ℃ and 180-250 rpm;
2) Adding composite reinforcing agent, carbon black, zinc oxide, stearic acid, anti-aging agent and coupling agent, and plasticating for 2-8min at 70-98 ℃ and 120-160 rpm;
3) Adding dicumyl peroxide, sulfur and accelerator, and plasticating at 75-90 deg.C and 110-155rpm for 4-15min; finally, triangular packaging, rolling, thinning and discharging to obtain rubber compound;
4) And vulcanizing the rubber compound at 145-170 ℃ and 10-20MPa for 20-45min to obtain the high-strength flame-retardant modified composite rubber.
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