CN115558179B - High-strength flame-retardant modified composite rubber - Google Patents
High-strength flame-retardant modified composite rubber Download PDFInfo
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Abstract
The invention discloses high-strength flame-retardant modified composite rubber, which comprises the following raw materials in parts by weight: 70-100 parts of carboxylated nitrile rubber; 24-45 parts by weight of ethylene propylene diene monomer rubber; 18-36 parts of chloroprene rubber; 3-12 parts by weight of dicumyl peroxide; 13-28 parts of flame-retardant reinforcing multi-effect auxiliary agent; 5-14 parts by weight of carbon black; 1-3.5 parts of sulfur; 2-5 parts of zinc oxide; 2-6 parts by weight of stearic acid; 1-3.5 parts by weight of an accelerator; 1.2-4 parts by weight of an anti-aging agent; 0.5 to 3.8 parts by weight of coupling agent. According to the invention, through the reinforcing and modifying effects of the flame-retardant reinforcing multi-effect auxiliary agent, the composite rubber with excellent strength and flame retardant property is prepared, and the flame-retardant reinforcing multi-effect auxiliary agent 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
Rubber materials are widely applied to various production fields, and in some application scenes, such as wires and cables, electronic devices and the like, high requirements are put on the strength and flame retardant property of rubber, and the traditional rubber is usually modified by adding other raw materials so as to improve the strength and flame retardant property. For example, patent CN104311931B discloses a high-strength aging-resistant abrasion-resistant flame-retardant composite rubber which is imparted with flame retardant property by adding an inorganic flame retardant of antimony trioxide, and the strength of which is improved by adding modified titanium dioxide, hard clay, reinforcing carbon black, kaolin and barite powder as reinforcing filler. However, the inorganic flame retardant antimony trioxide has the defects of poor compatibility with the rubber system and easy migration to the surface of the rubber system to fail, and the inorganic reinforcing filler has the defect of difficulty in being sufficiently dispersed in the organic rubber system, so that the modifiers are difficult to fully exert the effects in practice.
Therefore, there is a need in the art to improve upon the prior art to provide a more reliable solution.
Disclosure of Invention
The invention aims to solve the technical problem of providing the 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 following technical scheme: the high-strength flame-retardant modified composite rubber comprises the following raw materials in parts by weight:
preferably, 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 silica microspheres to obtain loaded microspheres;
s3, carrying out surface modification on the load microsphere;
s4, coating a hole sealing film on the load microsphere to obtain a functional microsphere;
s5, grafting the functional microspheres onto graphene oxide to obtain the flame-retardant reinforcing multi-effect auxiliary agent.
Preferably, the step S1 specifically includes:
s1-1, adding 4-12g of cetyltrimethylammonium 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, centrifugally filtering, and drying a solid product at 70-95 ℃ for 1-4h;
s1-3, and finally calcining at 580-700 ℃ for 6-10h to obtain the porous silica microspheres.
Preferably, the step S2 specifically includes:
s2-1, adding magnesium sulfate into deionized water, stirring, then adding the porous silica microspheres prepared in the step S1, and carrying out ultrasonic treatment for 30-60min to obtain a precursor liquid; wherein the mass ratio of the magnesium sulfate to the porous silicon dioxide microspheres is 4:1-1:1.5;
s2-2, dropwise adding ammonia water into the precursor liquid under continuous stirring, stopping dropwise adding after precipitation is not increased any more, 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-acrylic ester, and stirring for 10-45min;
s3-2, dropwise adding ammonia water under the protection of nitrogen, stirring for 6-12 hours at 45-65 ℃, centrifuging, washing a solid product with ethanol, and drying at 50-70 ℃ to obtain the surface modified load microsphere;
wherein the loaded microsphere: the mass ratio of the 3- (trimethoxysilyl) propyl-2-methyl-2-acrylic ester is 8:1-15:1.
Preferably, the step S4 specifically includes:
s4-1, adding the surface-modified load microsphere, cerium acetate and PVP into an ethanol water solution, and carrying out ultrasonic oscillation for 15-45min;
s4-2, adding styrene and AIBN, stirring for 6-15 hours at 60-90 ℃ under the protection of nitrogen, centrifuging, washing a solid product with ethanol, and vacuum drying at 60-90 ℃ to obtain the functional microsphere;
wherein, the surface modified load microsphere: cerium acetate with the mass ratio of 100:0.2-5.5, and surface modified load microsphere: the mass ratio of the styrene is 1:5-12.
Preferably, the step S5 specifically includes:
s5-1, adding graphene oxide into ethanol, and performing ultrasonic treatment for 30-90min to obtain graphene oxide dispersion liquid;
s5-2, adding the functional microspheres into an ethanol water solution, and performing ultrasonic treatment for 15-45min to obtain microsphere dispersion;
s5-3, mixing the graphene oxide dispersion liquid and the microsphere dispersion liquid, stirring at 65-80 ℃ for reaction for 6-14 hours, filtering after the reaction is finished, washing a solid product with ethanol, and 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 microsphere is 0.2-0.8:1.
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 silane coupling agent KH-560, silane coupling agent KH-570, silane coupling agent A-172 and silane coupling agent A-171, the anti-aging agent is one or a mixture of more of anti-aging agent 4020, anti-aging agent MC, anti-aging agent RD and anti-aging agent SP, and the accelerator is one or a mixture of more of accelerator EZ, accelerator MZ, accelerator M, accelerator DM and accelerator PZ.
Preferably, the preparation method of the high-strength flame-retardant modified composite rubber comprises the following steps:
1) Adding carboxylated 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 a 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 ℃ and 110-155rpm for 4-15min; finally, triangular packaging, rolling and thinning are performed, and then a piece is discharged to obtain a rubber compound;
4) Vulcanizing the mixed rubber 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 as follows:
according to the invention, through the reinforcing and modifying effects of the flame-retardant reinforcing multi-effect auxiliary agent, the composite rubber with excellent strength and flame retardant property is prepared, 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 into 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 flame retardance of the composite rubber material can be simultaneously achieved;
in the invention, porous silica microspheres with rich void structures are prepared firstly, 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 load microsphere by using a coupling agent 3- (trimethoxysilyl) propyl-2-methyl-2-acrylate, so that a double bond functional group capable of participating in a styrene polymerization reaction is grafted on the surface of the load microsphere; then coating a polystyrene film on the load microsphere by using a dispersion polymerization method, wherein cerium acetate is added in the step, so that cerium ions are connected to the load microsphere and are further doped into a film structure; and finally, connecting the functional microspheres to the surface of graphene oxide with a two-dimensional structure through the anchor point action of cerium ions, and constructing to obtain the flame-retardant reinforcing multi-effect auxiliary agent.
In the flame-retardant reinforcing multi-effect auxiliary agent structural system constructed by the invention, the reinforcing flame-retardant effect of the graphene oxide and the excellent flame retardant property of the magnesium hydroxide can be fully utilized, the interaction force between the graphene oxide and a rubber interface can be enhanced, meanwhile, 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 surface migration and easy to decompose and lose efficacy and the like are overcome, and the strength and the flame retardant property of the rubber can be obviously improved.
Detailed Description
The present invention is described in further detail below with reference to examples to enable those skilled in the art to practice the same by referring 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 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 were conducted under conventional conditions or conditions recommended by the manufacturer, without specifying the specific conditions. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The invention provides 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 silane coupling agent KH-560, silane coupling agent KH-570, silane coupling agent A-172 and silane coupling agent A-171, the anti-aging agent is one or a mixture of more of anti-aging agent 4020, anti-aging agent MC, anti-aging agent RD and anti-aging agent SP, and the accelerator is one or a mixture of more of accelerator EZ, accelerator MZ, accelerator M, accelerator DM and accelerator PZ.
In a preferred embodiment, the method for preparing the high-strength flame-retardant modified composite rubber comprises the following steps:
1) Adding carboxylated 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 a 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 ℃ and 110-155rpm for 4-15min; finally, triangular packaging, rolling and thinning are performed, and then a piece is discharged to obtain a rubber compound;
4) 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 is prepared by the following method:
s1, preparing porous silicon dioxide microspheres
S1-1, adding 4-12g of cetyltrimethylammonium 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, centrifugally filtering, and drying a solid product at 70-95 ℃ for 1-4h;
s1-3, and finally calcining at 580-700 ℃ for 6-10h to obtain the porous silica microspheres.
S2, preparing the load microsphere
S2-1, adding magnesium sulfate into deionized water, stirring, then adding the porous silica microspheres prepared in the step S1, and carrying out ultrasonic treatment for 30-60min to obtain a precursor liquid; wherein the mass ratio of the magnesium sulfate to the porous silicon dioxide microspheres is 4:1-1:1.5;
s2-2, dropwise adding ammonia water into the precursor liquid under continuous stirring, stopping dropwise adding after precipitation is not increased any more, filtering, washing a solid product, and drying to obtain the load microsphere.
S3, carrying out surface modification on the loaded microsphere
S3-1, adding the loaded microspheres into an ethanol water solution, adding 3- (trimethoxysilyl) propyl-2-methyl-2-acrylic ester, and stirring for 10-45min;
s3-2, dropwise adding ammonia water under the protection of nitrogen, stirring for 6-12 hours at 45-65 ℃, centrifuging, washing a solid product with ethanol, and drying at 50-70 ℃ to obtain the surface modified load microsphere;
wherein, load microballon: the mass ratio of the 3- (trimethoxysilyl) propyl-2-methyl-2-acrylic ester is 8:1-15:1.
S4, preparing functional microspheres
S4-1, adding the surface-modified load microsphere, cerium acetate and PVP into an ethanol water solution, and carrying out ultrasonic oscillation for 15-45min;
s4-2, adding styrene and AIBN, stirring for 6-15 hours at 60-90 ℃ under the protection of nitrogen, centrifuging, washing a solid product with ethanol, and vacuum drying at 60-90 ℃ to obtain the functional microsphere;
wherein, the surface modified load microsphere: cerium acetate with the mass ratio of 100:0.2-5.5, and surface modified load microsphere: the mass ratio of the styrene is 1:5-12.
S5, grafting the functional microsphere onto the graphene oxide
S5-1, adding graphene oxide into ethanol, and performing ultrasonic treatment for 30-90min to obtain graphene oxide dispersion liquid;
s5-2, adding the functional microspheres into an ethanol water solution, and performing ultrasonic treatment for 15-45min to obtain microsphere dispersion;
s5-3, mixing graphene oxide dispersion liquid and microsphere dispersion liquid, stirring at 65-80 ℃ for reaction for 6-14h, filtering after the reaction is finished, washing a solid product with ethanol, and vacuum drying at 55-75 ℃ to obtain a flame-retardant reinforcing multi-effect auxiliary agent;
wherein the mass ratio of the graphene oxide to the functional microsphere is 0.2-0.8:1.
According to the invention, the polarity is increased by introducing carboxyl into the carboxyl nitrile rubber, 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 and alkali corrosion resistance of the rubber can be further improved by compounding the ethylene propylene diene monomer rubber, 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 flame retardant performance of the composite rubber material, and can be fully dispersed into the rubber material system by constructing a graphene oxide composite system grafted with functional microspheres, so that the modifying and reinforcing effects of each functional component are effectively exerted, and the method is specific: 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 load microsphere by using a coupling agent 3- (trimethoxysilyl) propyl-2-methyl-2-acrylate, so that a double bond functional group capable of participating in a styrene polymerization reaction is grafted on the surface of the load microsphere; then coating a polystyrene film on the load microsphere by using a dispersion polymerization method, wherein cerium acetate is added in the step, so that cerium ions are connected to the load microsphere and are further doped into a film structure; and finally, connecting the functional microsphere to the surface of the graphene oxide with a two-dimensional structure through the anchor point action of cerium ions.
The inorganic flame retardant magnesium hydroxide can realize effective flame retardance by means of mechanisms such as chemical decomposition heat absorption and water release during heating, but has the defects of difficult dispersion, easy surface migration, easy decomposition failure and the like in an organic system, and the strength of the organic system is reduced when the addition amount is large due to the difficult dispersion. According to the invention, the defect of easy decomposition of the magnesium hydroxide is overcome by loading the magnesium hydroxide on the porous silicon dioxide microspheres, and further the magnesium hydroxide is coated and sealed by polystyrene, so that the magnesium hydroxide can realize long-term flame retardance (in normal use, the magnesium hydroxide is sealed in a gap structure of the silicon dioxide microspheres, isolated from a rubber system, does not influence the strength of the rubber system, and can keep flame retardance for a long time, and when the polystyrene film is heated to decompose and crack and the magnesium hydroxide overflows, the flame retardance of the magnesium hydroxide can be effectively exerted), and the magnesium hydroxide-loaded silicon dioxide microspheres can be uniformly dispersed in a matrix rubber system by virtue of the remarkable improvement effect of the polystyrene on the dispersion performance of the silicon dioxide microspheres in an organic system, so that the defects of difficult dispersion and easy surface migration of the magnesium hydroxide are overcome.
The silica microsphere is used as a carrier of the flame retardant, has certain flame retardant performance, and can improve the strength of rubber by virtue of the high strength and corrosion resistance of the microsphere.
When the polystyrene is coated, cerium ions added into the system can be connected to the microsphere through coordination with functional groups such as silicon hydroxyl groups on the surface of the silica microsphere, rare earth cerium has higher chemical activity, can provide a large number of coordination bonds, can form a multi-coordination complex with oxygen-containing functional groups such as hydroxyl groups and carboxyl groups, serves as an anchor point, and simultaneously coordinates with the functional groups such as the silicon hydroxyl groups of the silica microsphere and the carboxyl groups on the surface of the graphene oxide, so that the effect of bridging the silica microsphere and the graphene oxide is achieved; in addition, the rare earth cerium can also play a role in promoting the polymerization of styrene, and the rare earth cerium can form an active center to promote the polymerization reaction, so that a polystyrene coating film with a smooth and complete surface can be formed.
The polystyrene coating film can realize hole sealing and simultaneously can obviously improve the uniform dispersion performance of the silica microspheres in a rubber system.
After the polystyrene coated silica microspheres are grafted on the graphene oxide, the graphene oxide and the polystyrene coated silica microspheres can be fully dispersed in a rubber system through the improvement effect of the polystyrene on the compatibility of the silica microspheres and the rubber, so that 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 microsphere can serve as a network center point, so that the strength of the network structure can be improved, and the supplementing effect of the graphene oxide on the rubber strength is improved; meanwhile, the rare earth cerium in the flame-retardant reinforcing multi-effect auxiliary agent structural system can also form coordination bonds with carboxyl functional groups in the carboxyl nitrile rubber, so that the interface connection strength between the flame-retardant reinforcing multi-effect auxiliary agent system and the rubber system is further improved, and the overall strength of the rubber is further improved.
Wherein, 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 lamellar structure, can promote the generation of carbon residues in the combustion process, can serve as a physical barrier, can prevent heat transfer, and can delay pyrolysis products (generally combustible substances) from escaping from a matrix; (2) The graphene has a large specific surface area, can effectively adsorb inflammable pyrolysis products, and provides a carbonization platform; (3) The graphene surface contains abundant functional groups (groups such as carboxyl and hydroxyl groups), and the oxygen-containing functional groups decompose and dehydrate at high temperature, absorb ambient annealing amount and dilute ambient oxygen concentration, thereby inhibiting combustion.
According to the invention, by constructing a special flame-retardant reinforcing multi-effect auxiliary agent structural 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, meanwhile, the defects that the graphene oxide and magnesium hydroxide flame retardant is difficult to disperse in the rubber system, the magnesium hydroxide is easy to surface migration and easy to decompose and lose efficacy and the like are overcome, and the strength and flame retardant property of the rubber can be obviously improved.
Example 1
The high-strength flame-retardant modified composite rubber comprises the following raw materials in parts by weight:
wherein the coupling agent is silane coupling agent A-172, the anti-aging agent is a mixture of anti-aging agent MC and anti-aging agent RD, and the accelerator is a mixture of accelerator MZ and accelerator PZ.
The preparation method of the high-strength flame-retardant modified composite rubber comprises the following steps:
1) Adding carboxylated 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 a 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 plasticating at 80 ℃ and 135rpm for 7min; finally, triangular packaging, rolling and thinning are performed, and then a piece is discharged to obtain a rubber compound;
4) Vulcanizing the mixed rubber 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 steps:
s1, preparing porous silicon dioxide microspheres
S1-1, adding 5g of cetyltrimethylammonium bromide into 100g of ethanol water solution (the volume ratio of ethanol to water is 1:1), then adding 2.5g of ammonia water, and uniformly stirring;
s1-2, dropwise adding 6.4g of ethyl orthosilicate under continuous stirring, continuously stirring for 4 hours, centrifugally filtering, and drying a solid product at 75 ℃ for 2 hours;
s1-3, and finally calcining at 640 ℃ for 8 hours to obtain the porous silica microspheres.
S2, preparing the load microsphere
S2-1, adding magnesium sulfate into deionized water, stirring, then adding the porous silica microspheres prepared in the step S1, and carrying out ultrasonic treatment for 40min to obtain a precursor liquid; wherein the mass ratio of the magnesium sulfate to the porous silicon dioxide microspheres is 2.5:1;
s2-2, dropwise adding ammonia water with the concentration of 0.5mol/L into the precursor solution under continuous stirring, stopping dropwise adding after precipitation is not increased any more, 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 microsphere
S3-1, adding the loaded microspheres into an ethanol water solution (the volume ratio of ethanol to water is 1:1), adding 3- (trimethoxysilyl) propyl-2-methyl-2-acrylic ester (MPS), and stirring for 30min;
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 the surface modified load microsphere;
wherein, load microballon: the mass ratio of the 3- (trimethoxysilyl) propyl-2-methyl-2-acrylic ester is 12:1; ammonia water: the mass ratio of 3- (trimethoxysilyl) propyl-2-methyl-2-acrylate was 4:1.
S4, preparing functional microspheres
S4-1, adding the surface modified load microsphere, cerium acetate and PVP (polyvinylpyrrolidone) into an ethanol water solution (the volume ratio of ethanol to water is 3:1), and carrying out ultrasonic oscillation for 30min;
s4-2, adding styrene and AIBN (azodiisobutyronitrile), stirring for 12 hours at 75 ℃ under nitrogen protection, centrifuging, washing a solid product with ethanol, and vacuum drying at 60 ℃ to obtain functional microspheres;
wherein, the surface modified load microsphere: cerium acetate in the mass ratio of 100 to 1.2, and surface modified load microsphere: the mass ratio of the styrene is 1:8.
S5, grafting the functional microsphere onto the graphene oxide
S5-1, adding graphene oxide (purchased from Jiangsu Xianfeng nano materials science and technology Co., ltd., the same applies below) into ethanol, and performing ultrasonic treatment for 60min to obtain graphene oxide dispersion liquid;
s5-2, adding the functional microspheres into an ethanol water solution (the volume ratio of ethanol to water is 1:1), and performing ultrasonic treatment for 30min to obtain microsphere dispersion;
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 graphene oxide to the functional microsphere is 0.4:1.
Example 2
The high-strength flame-retardant modified composite rubber comprises the following raw materials in parts by weight:
wherein the coupling agent is silane coupling agent A-172, the anti-aging agent is a mixture of anti-aging agent MC and anti-aging agent RD, and the accelerator is a mixture of accelerator MZ and accelerator PZ.
The preparation method of the high-strength flame-retardant modified composite rubber comprises the following steps:
1) Adding carboxylated 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 a 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 plasticating at 80 ℃ and 135rpm for 7min; finally, triangular packaging, rolling and thinning are performed, and then a piece is discharged to obtain a rubber compound;
4) Vulcanizing the mixed rubber 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 steps:
s1, preparing porous silicon dioxide microspheres
S1-1, adding 5g of cetyltrimethylammonium bromide into 100g of ethanol water solution (the volume ratio of ethanol to water is 1:1), then adding 2.5g of ammonia water, and uniformly stirring;
s1-2, dropwise adding 6.4g of ethyl orthosilicate under continuous stirring, continuously stirring for 4 hours, centrifugally filtering, and drying a solid product at 75 ℃ for 2 hours;
s1-3, and finally calcining at 640 ℃ for 8 hours to obtain the porous silica microspheres.
S2, preparing the load microsphere
S2-1, adding magnesium sulfate into deionized water, stirring, then adding the porous silica microspheres prepared in the step S1, and carrying out ultrasonic treatment for 40min to obtain a precursor liquid; wherein the mass ratio of the magnesium sulfate to the porous silicon dioxide microspheres is 2.5:1;
s2-2, dropwise adding ammonia water with the concentration of 0.5mol/L into the precursor solution under continuous stirring, stopping dropwise adding after precipitation is not increased any more, 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 microsphere
S3-1, adding the loaded microspheres into an ethanol water solution (the volume ratio of ethanol to water is 1:1), adding 3- (trimethoxysilyl) propyl-2-methyl-2-acrylic ester (MPS), and stirring for 30min;
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 the surface modified load microsphere;
wherein, load microballon: the mass ratio of the 3- (trimethoxysilyl) propyl-2-methyl-2-acrylic ester is 12:1; ammonia water: the mass ratio of 3- (trimethoxysilyl) propyl-2-methyl-2-acrylate was 4:1.
S4, preparing functional microspheres
S4-1, adding the surface modified load microsphere, cerium acetate and PVP (polyvinylpyrrolidone) into an ethanol water solution (the volume ratio of ethanol to water is 3:1), and carrying out ultrasonic oscillation for 30min;
s4-2, adding styrene and AIBN (azodiisobutyronitrile), stirring for 12 hours at 75 ℃ under nitrogen protection, centrifuging, washing a solid product with ethanol, and vacuum drying at 60 ℃ to obtain functional microspheres;
wherein, the surface modified load microsphere: cerium acetate in the mass ratio of 100 to 1.2, and surface modified load microsphere: the mass ratio of the styrene is 1:8.
S5, grafting the functional microsphere onto the graphene oxide
S5-1, adding graphene oxide into ethanol, and performing ultrasonic treatment for 60 minutes to obtain graphene oxide dispersion liquid;
s5-2, adding the functional microspheres into an ethanol water solution (the volume ratio of ethanol to water is 1:1), and performing ultrasonic treatment for 30min to obtain microsphere dispersion;
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 graphene oxide to the functional microsphere is 0.4:1.
Example 3
The high-strength flame-retardant modified composite rubber comprises the following raw materials in parts by weight:
wherein the coupling agent is silane coupling agent A-172, the anti-aging agent is a mixture of anti-aging agent MC and anti-aging agent RD, and the accelerator is a mixture of accelerator MZ and accelerator PZ.
The preparation method of the high-strength flame-retardant modified composite rubber comprises the following steps:
1) Adding carboxylated 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 a 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 plasticating at 80 ℃ and 135rpm for 7min; finally, triangular packaging, rolling and thinning are performed, and then a piece is discharged to obtain a rubber compound;
4) Vulcanizing the mixed rubber 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 steps:
s1, preparing porous silicon dioxide microspheres
S1-1, adding 5g of cetyltrimethylammonium bromide into 100g of ethanol water solution (the volume ratio of ethanol to water is 1:1), then adding 2.5g of ammonia water, and uniformly stirring;
s1-2, dropwise adding 6.4g of ethyl orthosilicate under continuous stirring, continuously stirring for 4 hours, centrifugally filtering, and drying a solid product at 75 ℃ for 2 hours;
s1-3, and finally calcining at 640 ℃ for 8 hours to obtain the porous silica microspheres.
S2, preparing the load microsphere
S2-1, adding magnesium sulfate into deionized water, stirring, then adding the porous silica microspheres prepared in the step S1, and carrying out ultrasonic treatment for 40min to obtain a precursor liquid; wherein the mass ratio of the magnesium sulfate to the porous silicon dioxide microspheres is 2.5:1;
s2-2, dropwise adding ammonia water with the concentration of 0.5mol/L into the precursor solution under continuous stirring, stopping dropwise adding after precipitation is not increased any more, 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 microsphere
S3-1, adding the loaded microspheres into an ethanol water solution (the volume ratio of ethanol to water is 1:1), adding 3- (trimethoxysilyl) propyl-2-methyl-2-acrylic ester (MPS), and stirring for 30min;
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 the surface modified load microsphere;
wherein, load microballon: the mass ratio of the 3- (trimethoxysilyl) propyl-2-methyl-2-acrylic ester is 12:1; ammonia water: the mass ratio of 3- (trimethoxysilyl) propyl-2-methyl-2-acrylate was 4:1.
S4, preparing functional microspheres
S4-1, adding the surface modified load microsphere, cerium acetate and PVP (polyvinylpyrrolidone) into an ethanol water solution (the volume ratio of ethanol to water is 3:1), and carrying out ultrasonic oscillation for 30min;
s4-2, adding styrene and AIBN (azodiisobutyronitrile), stirring for 12 hours at 75 ℃ under nitrogen protection, centrifuging, washing a solid product with ethanol, and vacuum drying at 60 ℃ to obtain functional microspheres;
wherein, the surface modified load microsphere: cerium acetate in the mass ratio of 100 to 1.2, and surface modified load microsphere: the mass ratio of the styrene is 1:8.
S5, grafting the functional microsphere onto the graphene oxide
S5-1, adding graphene oxide into ethanol, and performing ultrasonic treatment for 60 minutes to obtain graphene oxide dispersion liquid;
s5-2, adding the functional microspheres into an ethanol water solution (the volume ratio of ethanol to water is 1:1), and performing ultrasonic treatment for 30min to obtain microsphere dispersion;
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 graphene oxide to the functional microsphere is 0.4:1.
Example 4
The high-strength flame-retardant modified composite rubber comprises the following raw materials in parts by weight:
wherein the coupling agent is silane coupling agent A-172, the anti-aging agent is a mixture of anti-aging agent MC and anti-aging agent RD, and the accelerator is a mixture of accelerator MZ and accelerator PZ.
The preparation method of the high-strength flame-retardant modified composite rubber comprises the following steps:
1) Adding carboxylated 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 a 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 plasticating at 80 ℃ and 135rpm for 7min; finally, triangular packaging, rolling and thinning are performed, and then a piece is discharged to obtain a rubber compound;
4) Vulcanizing the mixed rubber 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 steps:
s1, preparing porous silicon dioxide microspheres
S1-1, adding 5g of cetyltrimethylammonium bromide into 100g of ethanol water solution (the volume ratio of ethanol to water is 1:1), then adding 2.5g of ammonia water, and uniformly stirring;
s1-2, dropwise adding 6.4g of ethyl orthosilicate under continuous stirring, continuously stirring for 4 hours, centrifugally filtering, and drying a solid product at 75 ℃ for 2 hours;
s1-3, and finally calcining at 640 ℃ for 8 hours to obtain the porous silica microspheres.
S2, preparing the load microsphere
S2-1, adding magnesium sulfate into deionized water, stirring, then adding the porous silica microspheres prepared in the step S1, and carrying out ultrasonic treatment for 40min to obtain a precursor liquid; wherein the mass ratio of the magnesium sulfate to the porous silicon dioxide microspheres is 2.5:1;
s2-2, dropwise adding ammonia water with the concentration of 0.5mol/L into the precursor solution under continuous stirring, stopping dropwise adding after precipitation is not increased any more, 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 microsphere
S3-1, adding the loaded microspheres into an ethanol water solution (the volume ratio of ethanol to water is 1:1), adding 3- (trimethoxysilyl) propyl-2-methyl-2-acrylic ester (MPS), and stirring for 30min;
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 the surface modified load microsphere;
wherein, load microballon: the mass ratio of the 3- (trimethoxysilyl) propyl-2-methyl-2-acrylic ester is 12:1; ammonia water: the mass ratio of 3- (trimethoxysilyl) propyl-2-methyl-2-acrylate was 4:1.
S4, preparing functional microspheres
S4-1, adding the surface modified load microsphere, cerium acetate and PVP (polyvinylpyrrolidone) into an ethanol water solution (the volume ratio of ethanol to water is 3:1), and carrying out ultrasonic oscillation for 30min;
s4-2, adding styrene and AIBN (azodiisobutyronitrile), stirring for 12 hours at 75 ℃ under nitrogen protection, centrifuging, washing a solid product with ethanol, and vacuum drying at 60 ℃ to obtain functional microspheres;
wherein, the surface modified load microsphere: cerium acetate in the mass ratio of 100 to 1.8, and surface modified load microsphere: the mass ratio of the styrene is 1:8.
S5, grafting the functional microsphere onto the graphene oxide
S5-1, adding graphene oxide into ethanol, and performing ultrasonic treatment for 60 minutes to obtain graphene oxide dispersion liquid;
s5-2, adding the functional microspheres into an ethanol water solution (the volume ratio of ethanol to water is 1:1), and performing ultrasonic treatment for 30min to obtain microsphere dispersion;
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 graphene oxide to the functional microsphere is 0.4:1.
Comparative example 1
This example is substantially the same as example 2, except that the composite rubber in this example comprises the following raw materials in parts by weight:
comparative example 2
This example is substantially the same as example 2, except that the composite rubber in this example comprises the following raw materials in parts by weight:
comparative example 3
The example is basically the same as example 2, except that the flame-retardant reinforcing multi-effect auxiliary agent in the example is prepared by the following method:
s1, preparing porous silicon dioxide microspheres
S1-1, adding 5g of cetyltrimethylammonium bromide into 100g of ethanol water solution (the volume ratio of ethanol to water is 1:1), then adding 2.5g of ammonia water, and uniformly stirring;
s1-2, dropwise adding 6.4g of ethyl orthosilicate under continuous stirring, continuously stirring for 4 hours, centrifugally filtering, and drying a solid product at 75 ℃ for 2 hours;
s1-3, and finally calcining at 640 ℃ for 8 hours to obtain the porous silica microspheres.
S2, preparing the load microsphere
S2-1, adding magnesium sulfate into deionized water, stirring, then adding the porous silica microspheres prepared in the step S1, and carrying out ultrasonic treatment for 40min to obtain a precursor liquid; wherein the mass ratio of the magnesium sulfate to the porous silicon dioxide microspheres is 2.5:1;
s2-2, dropwise adding ammonia water with the concentration of 0.5mol/L into the precursor solution under continuous stirring, stopping dropwise adding after precipitation is not increased any more, 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 microsphere
S3-1, adding the loaded microspheres into an ethanol water solution (the volume ratio of ethanol to water is 1:1), adding 3- (trimethoxysilyl) propyl-2-methyl-2-acrylic ester (MPS), and stirring for 30min;
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 the surface modified load microsphere;
wherein, load microballon: the mass ratio of the 3- (trimethoxysilyl) propyl-2-methyl-2-acrylic ester is 12:1; ammonia water: the mass ratio of 3- (trimethoxysilyl) propyl-2-methyl-2-acrylate was 4:1.
S4, preparing functional microspheres
S4-1, adding the surface-modified load microsphere and PVP (polyvinylpyrrolidone) into an ethanol water solution (the volume ratio of ethanol to water is 3:1), and carrying out ultrasonic oscillation for 30min;
s4-2, adding styrene and AIBN (azodiisobutyronitrile), stirring for 12 hours at 75 ℃ under nitrogen protection, centrifuging, washing a solid product with ethanol, and vacuum drying at 60 ℃ to obtain functional microspheres;
wherein, the surface modified load microsphere: the mass ratio of the styrene is 1:8.
S5, grafting the functional microsphere onto the graphene oxide
S5-1, adding graphene oxide into ethanol, and performing ultrasonic treatment for 60 minutes to obtain graphene oxide dispersion liquid;
s5-2, adding the functional microspheres into an ethanol water solution (the volume ratio of ethanol to water is 1:1), and performing ultrasonic treatment for 30min to obtain microsphere dispersion;
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 graphene oxide to the functional microsphere is 0.4:1.
The composite 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. oxygen index testing was performed according to 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 likely to be ignited, representing the better flame retardance.
As can be seen from the results of table 1, the composite rubbers prepared in examples 1 to 4 have excellent strength and flame retardant properties; in comparative example 2, the defects of difficult dispersion of monomers such as graphite oxide, magnesium hydroxide and the like in a rubber system cannot be overcome, and the strength and the flame retardant property are obviously reduced; in comparative example 3, rare earth cerium with anchor point function 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.
Although embodiments of the present invention have been disclosed above, it is not limited to the use of the description and embodiments, it is well suited to various fields of use for the invention, and further modifications may be readily apparent to those skilled in the art, and accordingly, the invention is not limited to the particular details without departing from the general concepts defined in the claims and the equivalents thereof.
Claims (4)
1. The high-strength flame-retardant modified composite rubber is characterized by comprising the following raw materials in parts by weight:
70-100 parts of carboxylated nitrile rubber;
24-45 parts by weight of ethylene propylene diene monomer rubber;
18-36 parts of chloroprene rubber;
3-12 parts by weight of dicumyl peroxide;
13-28 parts of flame-retardant reinforcing multi-effect auxiliary agent;
5-14 parts by weight of carbon black;
1-3.5 parts of sulfur;
2-5 parts of zinc oxide;
2-6 parts by weight of stearic acid;
1-3.5 parts by weight of an accelerator;
1.2-4 parts by weight of an anti-aging agent;
0.5 to 3.8 parts by weight of a coupling agent;
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 silica microspheres to obtain loaded microspheres;
s3, carrying out surface modification on the load microsphere;
s4, coating a hole sealing film on the load microsphere to obtain a functional microsphere;
s5, grafting the functional microspheres onto graphene oxide to obtain the flame-retardant reinforcing multi-effect auxiliary agent;
the step S1 specifically includes:
s1-1, adding 4-12g of cetyltrimethylammonium 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, centrifugally filtering, and drying a solid product at 70-95 ℃ for 1-4h;
s1-3, and finally calcining at 580-700 ℃ for 6-10 hours to obtain the porous silica microspheres;
the step S2 specifically includes:
s2-1, adding magnesium sulfate into deionized water, stirring, then adding the porous silica microspheres prepared in the step S1, and carrying out ultrasonic treatment for 30-60min to obtain a precursor liquid; wherein the mass ratio of the magnesium sulfate to the porous silicon dioxide microspheres is 4:1-1:1.5;
s2-2, dropwise adding ammonia water into the precursor liquid under continuous stirring, stopping dropwise adding after precipitation is not increased any more, filtering, washing a solid product, and drying to obtain the load microsphere;
the step S3 specifically includes:
s3-1, adding the loaded microspheres into an ethanol water solution, adding 3- (trimethoxysilyl) propyl-2-methyl-2-acrylic ester, and stirring for 10-45min;
s3-2, dropwise adding ammonia water under the protection of nitrogen, stirring for 6-12 hours at 45-65 ℃, centrifuging, washing a solid product with ethanol, and drying at 50-70 ℃ to obtain the surface modified load microsphere;
wherein the loaded microsphere: the mass ratio of the 3- (trimethoxysilyl) propyl-2-methyl-2-acrylic ester is 8:1-15:1;
the step S4 specifically includes:
s4-1, adding the surface-modified load microsphere, cerium acetate and PVP into an ethanol water solution, and carrying out ultrasonic oscillation for 15-45min;
s4-2, adding styrene and AIBN, stirring for 6-15 hours at 60-90 ℃ under the protection of nitrogen, centrifuging, washing a solid product with ethanol, and vacuum drying at 60-90 ℃ to obtain the functional microsphere;
wherein, the surface modified load microsphere: cerium acetate with the mass ratio of 100:0.2-5.5, and surface modified load microsphere: the mass ratio of the styrene is 1:5-12;
the step S5 specifically includes:
s5-1, adding graphene oxide into ethanol, and performing ultrasonic treatment for 30-90min to obtain graphene oxide dispersion liquid;
s5-2, adding the functional microspheres into an ethanol water solution, and performing ultrasonic treatment for 15-45min to obtain microsphere dispersion;
s5-3, mixing the graphene oxide dispersion liquid and the microsphere dispersion liquid, stirring at 65-80 ℃ for reaction for 6-14 hours, filtering after the reaction is finished, washing a solid product with ethanol, and 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 microsphere is 0.2-0.8:1.
2. The high-strength flame-retardant modified composite rubber according to claim 1, which is characterized by comprising the following raw materials in parts by weight:
72 parts by weight of carboxylated nitrile rubber;
25 parts of ethylene propylene diene monomer rubber;
23 parts by weight of chloroprene rubber;
4 parts by weight of dicumyl peroxide;
18 parts by weight of a flame-retardant reinforcing multi-effect auxiliary;
7 parts by weight of carbon black;
1.5 parts of sulfur;
3 parts by weight of zinc oxide;
4 parts by weight of stearic acid;
2 parts of accelerator;
1.6 parts of an anti-aging agent;
1.2 parts by weight of a coupling agent.
3. The high-strength flame-retardant modified composite rubber according to claim 2, wherein the coupling agent is one or a mixture of 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 one or a mixture of more of antioxidant 4020, antioxidant MC, antioxidant RD and antioxidant SP, and the accelerator is one or a mixture of more of accelerator EZ, accelerator MZ, accelerator M, accelerator DM and accelerator PZ.
4. A high-strength flame-retardant modified composite rubber according to any one of claims 1 to 3, characterized in that the preparation method thereof comprises the steps of:
1) Adding carboxylated 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 a flame-retardant reinforcing multi-effect auxiliary 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 ℃ and 110-155rpm for 4-15min; finally, triangular packaging, rolling and thinning are performed, and then a piece is discharged to obtain a rubber compound;
4) Vulcanizing the mixed rubber at 145-170 ℃ and 10-20MPa for 20-45min to obtain the high-strength flame-retardant modified composite rubber.
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