CN112898644A - Flame-retardant corrosion-resistant rubber material and preparation method thereof - Google Patents

Flame-retardant corrosion-resistant rubber material and preparation method thereof Download PDF

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CN112898644A
CN112898644A CN202110113403.7A CN202110113403A CN112898644A CN 112898644 A CN112898644 A CN 112898644A CN 202110113403 A CN202110113403 A CN 202110113403A CN 112898644 A CN112898644 A CN 112898644A
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parts
flame
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rubber material
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陈泰辉
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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
    • C08L7/00—Compositions of natural rubber
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16—Fibres; Fibrils

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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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Abstract

The invention discloses a flame-retardant corrosion-resistant rubber material which comprises the following raw materials in parts by weight: 60-100 parts of natural rubber, 30-40 parts of chloroprene rubber, 10-15 parts of composite fiber, 5-10 parts of modified graphene oxide, 5-8 parts of polystyrene, 1-2 parts of vulcanizing agent, 2-4 parts of stearic acid, 3-5 parts of zinc oxide, 3-5 parts of anti-aging agent, 10-15 parts of paraffin and 1-3 parts of accelerator; the invention also discloses a preparation method of the flame-retardant corrosion-resistant rubber material, wherein natural rubber has good elasticity, cold resistance, wear resistance and electrical insulation, but the natural rubber has poor aging resistance, medium resistance and flame retardant property, and chloroprene rubber has excellent thermal aging resistance, ozonization resistance and weather aging resistance.

Description

Flame-retardant corrosion-resistant rubber material and preparation method thereof
Technical Field
The invention belongs to the technical field of rubber material preparation, and particularly relates to a flame-retardant corrosion-resistant rubber material and a preparation method thereof.
Background
The rubber is a high-elasticity polymer material with reversible deformation, is rich in elasticity at room temperature, can generate large deformation under the action of small external force, and can recover the original shape after the external force is removed. Rubber is a completely amorphous polymer with a low glass transition temperature (Tg) and a molecular weight often very high, greater than several hundred thousand. The rubber is a high-elasticity polymer, the molecular structure of the rubber is chain-shaped, the molecular chain has high flexibility, the molecular chain of the rubber is crosslinked (vulcanized), and the crosslinked material has the capability of rapid recovery when deformed under the action of external force, and has good physical and mechanical properties and chemical stability. The rubber can become a high-elasticity material with use value only through crosslinking, and is commonly called an eraser. Rubber is a basic raw material in the rubber industry and is widely used for manufacturing tires, rubber tubes, adhesive tapes, cables and other various rubber products. It is an important material as well as metal, chemical fiber, plastic, etc.
The rubber is not fireproof, but the problems that wires and cables are not fireproof and are inflammable when meeting fire in the existing fire accidents are solved, the field is lack of a fireproof rubber, the fireproof rubber is required to play a certain protection role in big fire, the loss of electricity brought to people in the fire can be reduced, the harm of electricity is reduced, and the temperature of corrosion, aging, hardening, inelasticity and the like of a cable skin can be caused by exposure of the cables and the wires to room temperature for a long time in the sun and rain, so that the improvement of the flame-retardant and corrosion-resistant rubber material is the technical problem to be solved at present.
Disclosure of Invention
The invention aims to provide a flame-retardant corrosion-resistant rubber material and a preparation method thereof.
The technical problems to be solved by the invention are as follows:
in the prior art, the application of rubber materials is limited in many fields due to poor fire resistance, poor heat resistance and poor corrosion resistance.
The purpose of the invention can be realized by the following technical scheme:
the flame-retardant corrosion-resistant rubber material comprises the following raw materials in parts by weight: 60-100 parts of natural rubber, 30-40 parts of chloroprene rubber, 10-15 parts of composite fiber, 5-10 parts of modified graphene oxide, 5-8 parts of polystyrene, 1-2 parts of vulcanizing agent, 2-4 parts of stearic acid, 3-5 parts of zinc oxide, 3-5 parts of anti-aging agent, 10-15 parts of paraffin and 1-3 parts of accelerator;
the flame-retardant corrosion-resistant rubber material is prepared by the following steps:
firstly, placing natural rubber into a 70 ℃ oven for baking for 12 hours, then cutting the natural rubber into strips, controlling the initial temperature of an internal mixer to be 80 ℃, controlling the rotating speed of a rotor to be 60r/min, putting a natural rubber strip and chloroprene rubber into the internal mixer, mixing for 20min, sequentially adding composite fibers, zinc oxide, modified graphene oxide and polystyrene into the internal mixer, continuously mixing for 30min, transferring the mixture to an open mill, adding a vulcanizing agent, stearic acid, an anti-aging agent, paraffin and an accelerator, and mixing for 30-50min to obtain a rubber compound;
and secondly, transferring the rubber compound obtained in the first step to a vulcanizing machine for molding, setting the pressure to be 10-12MPa, the temperature to be 150-180 ℃, the vulcanizing time to be 15-20min, and finally trimming and cutting to obtain the flame-retardant corrosion-resistant rubber material.
Further, the composite fiber is made by the following steps:
step S11, mixing melamine and formaldehyde solution with mass fraction of 55% according to the proportion of 1 mol: adding 250mL of 200-inch crude sodium chloride into a three-neck flask, stirring for 5min at the rotating speed of 80-100r/min, then adding a sodium hydroxide solution with the concentration of 1.0mol/L into the three-neck flask to adjust the pH value to 9, and stirring and reacting for 1-3h at the rotating speed of 500-inch crude sodium chloride/min under the heating of a water bath at the temperature of 70 ℃ to obtain a mixed solution A;
step S12, mixing antimony trioxide, absolute ethyl alcohol and deionized water according to the dosage ratio of 1-3 g: 90mL of: adding 10mL of the modified antimony trioxide into a beaker, performing ultrasonic dispersion for 10-20min at the frequency of 30-50kHz, adding a silane coupling agent KH-560 into the beaker, continuously reacting for 0.5h at constant frequency at room temperature, performing suction filtration, washing a filter cake for 3-5 times by using acetone, and finally drying in an oven at the temperature of 80 ℃ to constant weight to obtain the modified antimony trioxide;
step S13, adding an acetic acid solution with the mass fraction of 30% into the mixed solution A to adjust the pH value to 5, then adding modified antimony trioxide and magnesium hydroxide, controlling the reaction temperature to be 70-80 ℃, reacting at the rotation speed of 400-;
s14, adding N, N-dimethylacetamide and lithium chloride into a reaction kettle under the protection of nitrogen, adding 2- (4-aminophenyl) -5-aminobenzimidazole into the reaction kettle while stirring at the rotation speed of 200-300r/min, cooling to-5 ℃ after reacting for 30min, then adding isophthaloyl dichloride into the reaction kettle in an equivalent manner for three times at intervals of 5min, keeping the temperature of the reaction system not to exceed 30 ℃, continuing to react for 40min after the addition is finished, finally adding the composite material and lithium hydroxide obtained in the step S13, increasing the rotation speed to 300-500r/min, and reacting for 2-4h to obtain a spinning solution;
and S15, performing electrostatic spinning on the spinning solution obtained in the step S14 to obtain the modified fiber, wherein the spinning voltage is 18KV, the injection pump speed is 0.9mL/h, and the acceptance distance is 15 cm.
Further, the adding amount of the coupling agent KH-560 in the step S12 is 0.5-1% of the mass of the antimony trioxide, and the dosage ratio of the mixed solution A, the modified antimony trioxide and the magnesium hydroxide in the step S13 is 50-80 mL: 1 g: 3g of the total weight of the mixture; in step S14, the dosage ratio of N, N-dimethylacetamide, lithium chloride, 2- (4-aminophenyl) -5-aminobenzimidazole, isophthaloyl dichloride, the composite material and lithium hydroxide is 5L: 150g of: 672 g: 610 g: 5-8 g: 130 g.
The preparation method comprises the steps of modifying antimony trioxide by using a silane coupling agent KH-560, improving the dispersibility of the antimony trioxide in a polymer, enabling magnesium hydroxide to have the advantages of good stability, no toxicity, no harm, small smoke generation amount and the like, enabling the surface of the magnesium hydroxide to contain a large number of-OH hydrophilic groups and to be poor in compatibility with the polymer, preparing melamine formaldehyde resin coated magnesium hydroxide ions by adopting an in-situ polymerization method, blending the magnesium hydroxide ions with the modified antimony trioxide, combining the excellent heat resistance and waterproof performance of the polycyanularmine formaldehyde resin, filtering, washing and drying to obtain a composite material, then taking isophthaloyl dichloride and 2- (4-aminophenyl) -5-aminobenzimidazole as raw materials, taking N, N-dimethylacetamide as a solvent, taking the composite material as a filler, and preparing modified fibers by electrostatic spinning.
Further, the preparation method of the modified graphene oxide comprises the following steps:
step S21, mixing graphene oxide and deionized water according to the ratio of 1 g: adding 20-30mL of the graphene dispersion solution into a beaker, performing ultrasonic dispersion for 15-20min at the frequency of 30-50kHz to obtain a graphene dispersion solution, adding aniline and 5-aminosalicylic acid into the beaker, continuing performing ultrasonic dispersion for 1h under the condition of unchanged frequency to obtain a suspension, heating the suspension to 95 ℃ under the nitrogen atmosphere, preserving heat for 24h, cooling to room temperature, adding 50-60% of hydrochloric acid solution in volume fraction into the beaker, and adjusting the pH to 1 to obtain a mixture B;
and step S22, transferring the mixture B into an ice water bath, and mixing ammonium persulfate and deionized water according to the weight ratio of 10-11 g: adding 40mL of the initiator solution into a beaker, uniformly mixing to obtain an initiator solution, adding the initiator solution into a mixture B, stirring for 24 hours at the rotation speed of 300-400r/min, then adding a reinforcing agent into the mixture B, stirring for 24 hours at the constant rotation speed at the temperature of 58 ℃, finishing the reaction, carrying out vacuum filtration, washing a filter cake for 3-5 times by using absolute ethyl alcohol, drying for 24 hours at the temperature of 40-50 ℃ in a vacuum drying box, taking out, grinding and sieving by using a 400-mesh sieve to obtain the modified graphene oxide.
Further, in the step S21, the dosage ratio of the graphene dispersion liquid, aniline and 5-aminosalicylic acid is 30-50 mL: 1mL of: 1g of a compound; in the step S22, the reinforcing agent is ammonium persulfate and sulfuric acid according to the dosage ratio of 0.017 mol: 50mL, wherein the dosage ratio of the mixture B, the initiator solution and the reinforcing agent is 100 mL: 40-50mL and 50 mL.
Firstly, preparing graphene oxide dispersion liquid, then adding aniline and 5-aminosalicylic acid into the dispersion liquid, wherein the graphene oxide has a large specific surface area, epoxy groups and carboxyl groups on the graphene can form hydrogen bonds with amino groups in the aniline, aniline monomers are adsorbed on the graphene oxide and polymerized into polyaniline under the action of an initiator, the polyaniline can form a film layer with good compactness, the corrosion medium can be prevented from entering, and the hydroxyl groups and the carboxyl groups on the graphene can perform esterification reaction and differential hydrogen bonding with the hydroxyl groups and the carboxyl groups of the 5-aminosalicylic acid, so that the dispersibility of the graphene in the rubber material is improved.
Further, the vulcanizing agent is one or a mixture of a plurality of 2, 4-dichlorobenzoyl peroxide, 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane, benzoyl peroxide and diisophenylpropyl peroxide in any proportion.
Further, the anti-aging agent is one or two of N-phenyl-alpha-aniline and anti-aging agent 4020 which are mixed according to any proportion.
Further, the accelerator is one or more of thiuram accelerators, thiazole accelerators and sulfenamide accelerators which are mixed according to any proportion.
Further, the preparation method of the flame-retardant corrosion-resistant rubber material comprises the following steps:
firstly, placing natural rubber into a 70 ℃ oven for baking for 12 hours, then cutting the natural rubber into strips, controlling the initial temperature of an internal mixer to be 80 ℃, controlling the rotating speed of a rotor to be 60r/min, putting a natural rubber strip and chloroprene rubber into the internal mixer, mixing for 20min, sequentially adding composite fibers, zinc oxide, modified graphene oxide and polystyrene into the internal mixer, continuously mixing for 30min, transferring the mixture to an open mill, adding a vulcanizing agent, stearic acid, an anti-aging agent, paraffin and an accelerator, and mixing for 30-50min to obtain a rubber compound;
and secondly, transferring the rubber compound obtained in the first step to a vulcanizing machine for molding, setting the pressure to be 10-12MPa, the temperature to be 150-180 ℃, the vulcanizing time to be 15-20min, and finally trimming and cutting to obtain the flame-retardant corrosion-resistant rubber material.
The invention has the beneficial effects that:
the flame-retardant corrosion-resistant rubber material is prepared by taking natural rubber and chloroprene rubber as main materials, adding composite fibers, modified graphene oxide and zinc oxide as fillers, polystyrene as a toughening agent and other auxiliary agents, wherein the natural rubber has good elasticity, cold resistance, wear resistance and electrical insulation, but has poor aging resistance, medium resistance and flame retardance, more than 97% of chlorine atoms of the chloroprene rubber are connected to double-bond carbon, and the molecular chain structure is relatively stable, so that the chloroprene rubber has excellent heat aging resistance,The invention combines the advantages of two rubbers, adds composite fiber to endow rubber material with excellent flame retardant, corrosion resistance, shock resistance and other performances, wherein the modified fiber is prepared by electrostatic spinning of meta-position aromatic polyamide resin containing antimony trioxide, magnesium hydroxide and imidazole structure, wherein the antimony trioxide and the magnesium hydroxide are used as inorganic filler to cooperatively play flame retardant performance, the spinning solution contains benzimidazole structure, which not only forms a large conjugated system in the spinning solution to enhance the rigidity of the modified fiber, but also has extremely strong imidazole ring and amide group capable of interacting to form hydrogen bond (imidazole and imidazole, amide and amide, imidazole and amide) and carrying out layered arrangement, so that the intermolecular force is further strengthened, the mechanical performance of the modified fiber is improved, and the modified fiber has excellent heat resistance, on one hand, the inorganic composite material is added, and on the other hand, because the modified fiber contains a large number of amido bonds, the modified fiber is thermally decomposed in flame to release NO and CO2、H2The introduction of imidazole structure not only reduces the content of hydrogen atoms of main combustion source, but also introduces benzimidazole with better heat resistance and easier char formation, and simultaneously, similar to thermal oxidative degradation, imidazole ring can capture active free radicals generated in the thermal oxidative degradation process and produce water and N2The composite rubber material has excellent flame retardant performance, the modified graphene oxide can better play a shielding effect, the time for corrosive media to enter the rubber material is prolonged, pores and defects in the rubber material are filled, the corrosion resistance of the rubber material is improved, and when the rubber material is impacted, a stress concentration point can be used for absorbing a part of impact quantity, and the impact resistance of the rubber material is improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The flame-retardant corrosion-resistant rubber material comprises the following raw materials in parts by weight: 60 parts of natural rubber, 30 parts of chloroprene rubber, 10 parts of composite fiber, 5 parts of modified graphene oxide, 5 parts of polystyrene, 1 part of vulcanizing agent, 2 parts of stearic acid, 3 parts of zinc oxide, 3 parts of anti-aging agent, 10 parts of paraffin and 1 part of accelerator;
the flame-retardant corrosion-resistant rubber material is prepared by the following steps:
firstly, placing natural rubber into a 70 ℃ oven for baking for 12 hours, then cutting the natural rubber into strips, controlling the initial temperature of an internal mixer to be 80 ℃, controlling the rotating speed of a rotor to be 60r/min, putting a natural rubber strip and chloroprene rubber into the internal mixer, mixing for 20min, sequentially adding composite fibers, zinc oxide, modified graphene oxide and polystyrene into the internal mixer, continuously mixing for 30min, transferring the mixture to an open mill, adding a vulcanizing agent, stearic acid, an anti-aging agent, paraffin and an accelerator, and mixing for 30min to obtain a rubber compound;
and secondly, transferring the mixed rubber obtained in the first step to a vulcanizing machine for molding, setting the pressure to be 10MPa, the temperature to be 150 ℃, the vulcanizing time to be 15min, and finally trimming and cutting to obtain the flame-retardant corrosion-resistant rubber material.
The composite fiber is prepared by the following steps:
step S11, mixing melamine and formaldehyde solution with mass fraction of 55% according to the proportion of 1 mol: adding 200mL of the mixed solution into a three-neck flask, stirring for 5min under the condition of the rotating speed of 80r/min, then adding a sodium hydroxide solution with the concentration of 1.0mol/L into the three-neck flask to adjust the pH value to 9, and stirring and reacting for 1h under the heating condition of a water bath at the temperature of 70 ℃ and the rotating speed of 500r/min to obtain a mixed solution A;
step S12, mixing antimony trioxide, absolute ethyl alcohol and deionized water according to the dosage ratio of 1 g: 90mL of: adding 10mL of the modified antimony trioxide into a beaker, performing ultrasonic dispersion for 10min at the frequency of 30kHz, adding a silane coupling agent KH-560 into the beaker, continuously reacting for 0.5h at room temperature with constant frequency, performing suction filtration, washing a filter cake for 3 times by using acetone, and finally drying in an oven at the temperature of 80 ℃ to constant weight to obtain the modified antimony trioxide;
step S13, adding an acetic acid solution with the mass fraction of 30% into the mixed solution A to adjust the pH value to 5, then adding modified antimony trioxide and magnesium hydroxide, controlling the reaction temperature to be 70 ℃, reacting at the rotating speed of 400r/min for 1h, filtering after the reaction is finished, washing a filter cake for 3 times by using an ethanol solution with the mass fraction of 35%, and drying in a drying oven at the temperature of 100 ℃ for 8h to obtain the composite material;
s14, adding N, N-dimethylacetamide and lithium chloride into a reaction kettle under the protection of nitrogen, adding 2- (4-aminophenyl) -5-aminobenzimidazole into the reaction kettle while stirring at the rotating speed of 200r/min, cooling to minus 5 ℃ after reacting for 30min, then adding isophthaloyl dichloride into the reaction kettle in an equivalent manner for three times at intervals of 5min, keeping the temperature of a reaction system not to exceed 30 ℃, continuing to react for 40min after the addition is finished, finally adding the composite material obtained in the step S13 and lithium hydroxide, increasing the rotating speed to 300r/min, and reacting for 2h to obtain a spinning solution;
and S15, performing electrostatic spinning on the spinning solution obtained in the step S14 to obtain the modified fiber, wherein the spinning voltage is 18KV, the injection pump speed is 0.9mL/h, and the acceptance distance is 15 cm.
In the step S12, the addition amount of the coupling agent KH-560 is 0.5 percent of the mass of the antimony trioxide, and the dosage ratio of the mixed solution A, the modified antimony trioxide and the magnesium hydroxide in the step S13 is 50mL: 1 g: 3g of the total weight of the mixture; in step S14, the dosage ratio of N, N-dimethylacetamide, lithium chloride, 2- (4-aminophenyl) -5-aminobenzimidazole, isophthaloyl dichloride, the composite material and lithium hydroxide is 5L: 150g of: 672 g: 610 g: 5 g: 130 g.
The preparation method of the modified graphene oxide comprises the following steps:
step S21, mixing graphene oxide and deionized water according to the ratio of 1 g: adding 20mL of the graphene dispersion solution into a beaker, performing ultrasonic dispersion for 15min at the frequency of 30kHz to obtain graphene dispersion solution, then adding aniline and 5-aminosalicylic acid into the beaker, continuing ultrasonic dispersion for 1h under the condition of unchanged frequency to obtain suspension, heating the suspension to 95 ℃ under the nitrogen atmosphere, preserving heat for 24h, cooling to room temperature, adding 50% by volume of hydrochloric acid solution into the beaker, and adjusting the pH value to 1 to obtain a mixture B;
and step S22, transferring the mixture B into an ice water bath, and mixing ammonium persulfate and deionized water according to the weight ratio of 10 g: adding 40mL of the initiator solution into a beaker, uniformly mixing to obtain an initiator solution, adding the initiator solution into the mixture B, stirring for 24 hours at the rotating speed of 300r/min, then adding a reinforcing agent into the mixture B, stirring for 24 hours at the constant rotating speed at the temperature of 58 ℃, finishing the reaction, carrying out vacuum filtration, washing a filter cake for 3 times by using absolute ethyl alcohol, drying for 24 hours at the temperature of 40 ℃ in a vacuum drying oven, then taking out, grinding and sieving by using a 400-mesh sieve to obtain the modified graphene oxide.
The using amount ratio of the graphene dispersion liquid, the aniline and the 5-aminosalicylic acid in the step S21 is 30 mL: 1mL of: 1g of a compound; in the step S22, the reinforcing agent is ammonium persulfate and sulfuric acid according to the dosage ratio of 0.017 mol: 50mL, wherein the dosage ratio of the mixture B, the initiator solution and the reinforcing agent is 100 mL: 40mL and 50 mL.
The vulcanizing agent is 2, 4-dichlorobenzoyl peroxide, the anti-aging agent is N-phenyl-alpha-aniline, and the accelerator is a sulfonamide accelerator.
Example 2
The flame-retardant corrosion-resistant rubber material comprises the following raw materials in parts by weight: 80 parts of natural rubber, 35 parts of chloroprene rubber, 12 parts of composite fiber, 8 parts of modified graphene oxide, 7 parts of polystyrene, 1.5 parts of vulcanizing agent, 3 parts of stearic acid, 4 parts of zinc oxide, 4 parts of anti-aging agent, 13 parts of paraffin and 2 parts of accelerator;
the flame-retardant corrosion-resistant rubber material is prepared by the following steps:
firstly, placing natural rubber into a 70 ℃ oven for baking for 12 hours, then cutting the natural rubber into strips, controlling the initial temperature of an internal mixer to be 80 ℃, controlling the rotating speed of a rotor to be 60r/min, putting a natural rubber strip and chloroprene rubber into the internal mixer, mixing for 20min, sequentially adding composite fibers, zinc oxide, modified graphene oxide and polystyrene into the internal mixer, continuously mixing for 30min, transferring the mixture to an open mill, adding a vulcanizing agent, stearic acid, an anti-aging agent, paraffin and an accelerator, and mixing for 40min to obtain a mixed rubber;
and secondly, transferring the mixed rubber obtained in the first step to a vulcanizing machine for molding, setting the pressure to be 11MPa, the temperature to be 170 ℃, the vulcanizing time to be 18min, and finally trimming and cutting to obtain the flame-retardant corrosion-resistant rubber material.
The composite fiber is prepared by the following steps:
step S11, mixing melamine and formaldehyde solution with mass fraction of 55% according to the proportion of 1 mol: 230mL of the solution is added into a three-neck flask, the solution is stirred for 5min under the condition of the rotating speed of 90r/min, then a sodium hydroxide solution with the concentration of 1.0mol/L is added into the three-neck flask to adjust the pH value to 9, and the solution is stirred and reacted for 2h under the heating condition of a water bath at the temperature of 70 ℃ and the rotating speed of 550r/min to obtain a mixed solution A;
step S12, mixing antimony trioxide, absolute ethyl alcohol and deionized water according to the dosage ratio of 2 g: 90mL of: adding 10mL of the modified antimony trioxide into a beaker, performing ultrasonic dispersion for 15min at the frequency of 40kHz, adding a silane coupling agent KH-560 into the beaker, continuously reacting for 0.5h at room temperature with constant frequency, performing suction filtration, washing a filter cake for 4 times by using acetone, and finally drying in an oven at the temperature of 80 ℃ to constant weight to obtain the modified antimony trioxide;
step S13, adding an acetic acid solution with the mass fraction of 30% into the mixed solution A to adjust the pH value to 5, then adding modified antimony trioxide and magnesium hydroxide, controlling the reaction temperature to be 75 ℃, reacting at the rotating speed of 500r/min for 2 hours, filtering after the reaction is finished, washing a filter cake for 4 times by using an ethanol solution with the mass fraction of 35%, and drying in an oven at the temperature of 105 ℃ for 9 hours to obtain a composite material;
s14, adding N, N-dimethylacetamide and lithium chloride into a reaction kettle under the protection of nitrogen, adding 2- (4-aminophenyl) -5-aminobenzimidazole into the reaction kettle while stirring at a rotating speed of 250r/min, cooling to minus 5 ℃ after reacting for 30min, then adding isophthaloyl dichloride into the reaction kettle in an equivalent manner for three times at intervals of 5min, keeping the temperature of a reaction system not to exceed 30 ℃, continuing to react for 40min after the addition is finished, finally adding the composite material obtained in the step S13 and lithium hydroxide, increasing the rotating speed to 400r/min, and reacting for 3h to obtain a spinning solution;
and S15, performing electrostatic spinning on the spinning solution obtained in the step S14 to obtain the modified fiber, wherein the spinning voltage is 18KV, the injection pump speed is 0.9mL/h, and the acceptance distance is 15 cm.
In the step S12, the addition amount of the coupling agent KH-560 is 0.8 percent of the mass of the antimony trioxide, and the dosage ratio of the mixed solution A, the modified antimony trioxide and the magnesium hydroxide in the step S13 is 70 mL: 1 g: 3g of the total weight of the mixture; in step S14, the dosage ratio of N, N-dimethylacetamide, lithium chloride, 2- (4-aminophenyl) -5-aminobenzimidazole, isophthaloyl dichloride, the composite material and lithium hydroxide is 5L: 150g of: 672 g: 610 g: 7 g: 130 g.
The preparation method of the modified graphene oxide comprises the following steps:
step S21, mixing graphene oxide and deionized water according to the ratio of 1 g: adding 25mL of the graphene dispersion solution into a beaker, performing ultrasonic dispersion for 18min at the frequency of 40kHz to obtain graphene dispersion solution, then adding aniline and 5-aminosalicylic acid into the beaker, continuing performing ultrasonic dispersion for 1h under the condition of unchanged frequency to obtain suspension, heating the suspension to 95 ℃ under the nitrogen atmosphere, preserving heat for 24h, cooling to room temperature, adding 55 volume percent hydrochloric acid solution into the beaker, and adjusting the pH value to 1 to obtain a mixture B;
and step S22, transferring the mixture B into an ice water bath, and mixing ammonium persulfate and deionized water according to the weight ratio of 10 g: adding 40mL of the initiator solution into a beaker, uniformly mixing to obtain an initiator solution, adding the initiator solution into the mixture B, stirring for 24 hours at the rotating speed of 350r/min, then adding a reinforcing agent into the mixture B, stirring for 24 hours at the constant rotating speed at the temperature of 58 ℃, finishing the reaction, carrying out vacuum filtration, washing a filter cake for 4 times by using absolute ethyl alcohol, drying for 24 hours at the temperature of 45 ℃ in a vacuum drying oven, then taking out, grinding and sieving by using a 400-mesh sieve to obtain the modified graphene oxide.
The using amount ratio of the graphene dispersion liquid, the aniline and the 5-aminosalicylic acid in the step S21 is 40mL: 1mL of: 1g of a compound; in the step S22, the reinforcing agent is ammonium persulfate and sulfuric acid according to the dosage ratio of 0.017 mol: 50mL, wherein the dosage ratio of the mixture B, the enhancer solution and the accelerant is 100 mL: 45mL and 50 mL.
The vulcanizing agent is 2, 4-dichlorobenzoyl peroxide, the anti-aging agent is N-phenyl-alpha-aniline, and the accelerator is a sulfonamide accelerator.
Example 3
The flame-retardant corrosion-resistant rubber material comprises the following raw materials in parts by weight: 60-100 parts of natural rubber, 40 parts of chloroprene rubber, 15 parts of composite fiber, 10 parts of modified graphene oxide, 8 parts of polystyrene, 2 parts of vulcanizing agent, 4 parts of stearic acid, 5 parts of zinc oxide, 5 parts of anti-aging agent, 15 parts of paraffin and 3 parts of accelerator;
the flame-retardant corrosion-resistant rubber material is prepared by the following steps:
firstly, placing natural rubber into a 70 ℃ oven for baking for 12 hours, then cutting the natural rubber into strips, controlling the initial temperature of an internal mixer to be 80 ℃, controlling the rotating speed of a rotor to be 60r/min, putting a natural rubber strip and chloroprene rubber into the internal mixer, mixing for 20min, sequentially adding composite fibers, zinc oxide, modified graphene oxide and polystyrene into the internal mixer, continuously mixing for 30min, transferring the mixture to an open mill, adding a vulcanizing agent, stearic acid, an anti-aging agent, paraffin and an accelerator, and mixing for 50min to obtain a mixed rubber;
and secondly, transferring the mixed rubber obtained in the first step to a vulcanizing machine for molding, setting the pressure to be 12MPa, the temperature to be 180 ℃, the vulcanizing time to be 20min, and finally trimming and cutting to obtain the flame-retardant corrosion-resistant rubber material.
The composite fiber is prepared by the following steps:
step S11, mixing melamine and formaldehyde solution with mass fraction of 55% according to the proportion of 1 mol: adding 250mL of the mixed solution into a three-neck flask, stirring for 5min at the rotation speed of 100r/min, then adding a sodium hydroxide solution with the concentration of 1.0mol/L into the three-neck flask to adjust the pH value to 9, and stirring and reacting for 3h at the rotation speed of 600r/min under the heating of a water bath condition at the temperature of 70 ℃ to obtain a mixed solution A;
step S12, mixing antimony trioxide, absolute ethyl alcohol and deionized water according to the dosage ratio of 3 g: 90mL of: adding 10mL of the modified antimony trioxide into a beaker, performing ultrasonic dispersion at the frequency of 50kHz for 20min, adding a silane coupling agent KH-560 into the beaker, continuously reacting for 0.5h at room temperature with constant frequency, performing suction filtration, washing a filter cake for 5 times by using acetone, and finally drying in an oven at the temperature of 80 ℃ to constant weight to obtain the modified antimony trioxide;
step S13, adding an acetic acid solution with the mass fraction of 30% into the mixed solution A to adjust the pH value to 5, then adding modified antimony trioxide and magnesium hydroxide, controlling the reaction temperature to be 80 ℃, reacting at the rotating speed of 600r/min for 1-3h, filtering after the reaction is finished, washing a filter cake for 5 times by using an ethanol solution with the mass fraction of 35%, and drying in a drying oven at the temperature of 110 ℃ for 10h to obtain the composite material;
s14, adding N, N-dimethylacetamide and lithium chloride into a reaction kettle under the protection of nitrogen, adding 2- (4-aminophenyl) -5-aminobenzimidazole into the reaction kettle while stirring at the rotating speed of 300r/min, cooling to minus 5 ℃ after reacting for 30min, then adding isophthaloyl dichloride into the reaction kettle in an equivalent manner for three times, wherein the interval is 5min each time, the temperature of a reaction system is kept not more than 30 ℃, continuing to react for 40min after the addition is finished, finally adding the composite material obtained in the step S13 and lithium hydroxide, increasing the rotating speed to 500r/min, and reacting for 4h to obtain a spinning solution;
and S15, performing electrostatic spinning on the spinning solution obtained in the step S14 to obtain the modified fiber, wherein the spinning voltage is 18KV, the injection pump speed is 0.9mL/h, and the acceptance distance is 15 cm.
In the step S12, the addition amount of the coupling agent KH-560 is 1% of the mass of the antimony trioxide, and the dosage ratio of the mixed solution A, the modified antimony trioxide and the magnesium hydroxide in the step S13 is 80 mL: 1 g: 3g of the total weight of the mixture; in step S14, the dosage ratio of N, N-dimethylacetamide, lithium chloride, 2- (4-aminophenyl) -5-aminobenzimidazole, isophthaloyl dichloride, the composite material and lithium hydroxide is 5L: 150g of: 672 g: 610 g: 8 g: 130 g.
The preparation method of the modified graphene oxide comprises the following steps:
step S21, mixing graphene oxide and deionized water according to the ratio of 1 g: adding 30mL of the graphene dispersion solution into a beaker, performing ultrasonic dispersion for 20min at the frequency of 350kHz to obtain graphene dispersion solution, then adding aniline and 5-aminosalicylic acid into the beaker, continuing ultrasonic dispersion for 1h under the condition of unchanged frequency to obtain suspension, heating the suspension to 95 ℃ under the nitrogen atmosphere, preserving heat for 24h, cooling to room temperature, adding hydrochloric acid solution with volume fraction of 60 into the beaker, and adjusting the pH value to 1 to obtain a mixture B;
and step S22, transferring the mixture B into an ice water bath, and mixing ammonium persulfate and deionized water according to the weight ratio of 11 g: adding 40mL of the initiator solution into a beaker, uniformly mixing to obtain an initiator solution, adding the initiator solution into the mixture B, stirring for 24 hours at the rotating speed of 400r/min, then adding a reinforcing agent into the mixture B, stirring for 24 hours at the constant rotating speed at the temperature of 58 ℃, finishing the reaction, carrying out vacuum filtration, washing a filter cake for 5 times by using absolute ethyl alcohol, drying for 24 hours at the temperature of 50 ℃ in a vacuum drying oven, taking out, grinding and sieving by using a 400-mesh sieve to obtain the modified graphene oxide.
In the step S21, the dosage ratio of the graphene dispersion liquid to the aniline to the 5-aminosalicylic acid is 50mL: 1mL of: 1g of a compound; in the step S22, the accelerator enhancer is ammonium persulfate and sulfuric acid according to the dosage ratio of 0.017 mol: 50mL, wherein the dosage ratio of the mixture B, the initiator solution and the reinforcing agent is 100 mL:50 mL:50 mL.
The vulcanizing agent is 2, 4-dichlorobenzoyl peroxide, the anti-aging agent is N-phenyl-alpha-aniline, and the accelerator is a sulfonamide accelerator.
Comparative example 1
The composite fiber in example 1 was removed, and the rest of the raw materials and the preparation process were unchanged.
Comparative example 2
The modified graphene oxide in example 2 was removed, and the remaining raw materials and the preparation process were unchanged.
Comparative example 3
The comparative example is a common flame-retardant corrosion-resistant rubber material in the market.
The rubber materials of examples 1-3 and comparative examples 1-3 are subjected to performance tests, and oxygen indexes GB/T2406-2008, a method in an oxygen index method for a plastic combustion performance test method; the tensile strength is tested according to the method of GB/T1040.2-92 Plastic tensile Property test method; the elongation at break is tested according to the method in GB/T1040.2-92 Plastic tensile Property test method; for corrosion resistance, soaking each group of rubber materials in a sodium hydroxide solution with the mass fraction of 60% for 500 hours and soaking in a sodium hydroxide solution with the mass fraction of 80% for 500 hours, observing the change of the rubber materials, and testing results are shown in the following table:
Figure BDA0002919786650000141
as can be seen from the above table, the test results of the rubber materials of examples 1-3 are superior to those of comparative examples 1-3 in the processes of oxygen index test, mechanical property test and corrosion resistance test, which shows that the rubber materials prepared by the invention not only have excellent flame retardant property, but also have excellent mechanical property and corrosion resistance.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.

Claims (9)

1. The flame-retardant corrosion-resistant rubber material is characterized by comprising the following raw materials in parts by weight: 60-100 parts of natural rubber, 30-40 parts of chloroprene rubber, 10-15 parts of composite fiber, 5-10 parts of modified graphene oxide, 5-8 parts of polystyrene, 1-2 parts of vulcanizing agent, 2-4 parts of stearic acid, 3-5 parts of zinc oxide, 3-5 parts of anti-aging agent, 10-15 parts of paraffin and 1-3 parts of accelerator;
the flame-retardant corrosion-resistant rubber material is prepared by the following steps:
firstly, placing natural rubber into a 70 ℃ oven for baking for 12 hours, then cutting the natural rubber into strips, controlling the initial temperature of an internal mixer to be 80 ℃, controlling the rotating speed of a rotor to be 60r/min, putting a natural rubber strip and chloroprene rubber into the internal mixer, mixing for 20min, sequentially adding composite fibers, zinc oxide, modified graphene oxide and polystyrene into the internal mixer, continuously mixing for 30min, transferring the mixture to an open mill, adding a vulcanizing agent, stearic acid, an anti-aging agent, paraffin and an accelerator, and mixing for 30-50min to obtain a rubber compound;
and secondly, transferring the rubber compound obtained in the first step to a vulcanizing machine for molding, setting the pressure to be 10-12MPa, the temperature to be 150-180 ℃, the vulcanizing time to be 15-20min, and finally trimming and cutting to obtain the flame-retardant corrosion-resistant rubber material.
2. The flame-retardant corrosion-resistant rubber material according to claim 1, wherein the composite fiber is prepared by the following steps:
step S11, mixing melamine and formaldehyde solution with mass fraction of 55% according to the proportion of 1 mol: adding 250mL of 200-inch crude sodium chloride into a three-neck flask, stirring for 5min at the rotating speed of 80-100r/min, then adding a sodium hydroxide solution with the concentration of 1.0mol/L into the three-neck flask to adjust the pH value to 9, and stirring and reacting for 1-3h at the rotating speed of 500-inch crude sodium chloride/min under the heating of a water bath at the temperature of 70 ℃ to obtain a mixed solution A;
step S12, mixing antimony trioxide, absolute ethyl alcohol and deionized water according to the dosage ratio of 1-3 g: 90mL of: adding 10mL of the modified antimony trioxide into a beaker, performing ultrasonic dispersion for 10-20min at the frequency of 30-50kHz, adding a silane coupling agent KH-560 into the beaker, continuously reacting for 0.5h at constant frequency at room temperature, performing suction filtration, washing a filter cake for 3-5 times by using acetone, and finally drying in an oven at the temperature of 80 ℃ to constant weight to obtain the modified antimony trioxide;
step S13, adding an acetic acid solution with the mass fraction of 30% into the mixed solution A to adjust the pH value to 5, then adding modified antimony trioxide and magnesium hydroxide, controlling the reaction temperature to be 70-80 ℃, reacting at the rotation speed of 400-;
s14, adding N, N-dimethylacetamide and lithium chloride into a reaction kettle under the protection of nitrogen, adding 2- (4-aminophenyl) -5-aminobenzimidazole into the reaction kettle while stirring at the rotation speed of 200-300r/min, cooling to-5 ℃ after reacting for 30min, then adding isophthaloyl dichloride into the reaction kettle in an equivalent manner for three times at intervals of 5min, keeping the temperature of the reaction system not to exceed 30 ℃, continuing to react for 40min after the addition is finished, finally adding the composite material and lithium hydroxide obtained in the step S13, increasing the rotation speed to 300-500r/min, and reacting for 2-4h to obtain a spinning solution;
and S15, performing electrostatic spinning on the spinning solution obtained in the step S14 to obtain the modified fiber, wherein the spinning voltage is 18KV, the injection pump speed is 0.9mL/h, and the acceptance distance is 15 cm.
3. The flame-retardant corrosion-resistant rubber material according to claim 2, wherein the amount of the coupling agent KH-560 added in step S12 is 0.5-1% of the mass of antimony trioxide, and the amount ratio of the mixed solution A, the modified antimony trioxide and the magnesium hydroxide used in step S13 is 50-80 mL: 1 g: 3g of the total weight of the mixture; in step S14, the dosage ratio of N, N-dimethylacetamide, lithium chloride, 2- (4-aminophenyl) -5-aminobenzimidazole, isophthaloyl dichloride, the composite material and lithium hydroxide is 5L: 150g of: 672 g: 610 g: 5-8 g: 130 g.
4. The flame-retardant corrosion-resistant rubber material according to claim 1, wherein the preparation method of the modified graphene oxide comprises the following steps:
step S21, mixing graphene oxide and deionized water according to the ratio of 1 g: adding 20-30mL of the graphene dispersion solution into a beaker, performing ultrasonic dispersion for 15-20min at the frequency of 30-50kHz to obtain a graphene dispersion solution, adding aniline and 5-aminosalicylic acid into the beaker, continuing performing ultrasonic dispersion for 1h under the condition of unchanged frequency to obtain a suspension, heating the suspension to 95 ℃ under the nitrogen atmosphere, preserving heat for 24h, cooling to room temperature, adding 50-60% of hydrochloric acid solution in volume fraction into the beaker, and adjusting the pH to 1 to obtain a mixture B;
and step S22, transferring the mixture B into an ice water bath, and mixing ammonium persulfate and deionized water according to the weight ratio of 10-11 g: adding 40mL of the initiator solution into a beaker, uniformly mixing to obtain an initiator solution, adding the initiator solution into a mixture B, stirring for 24 hours at the rotation speed of 300-400r/min, then adding a reinforcing agent into the mixture B, stirring for 24 hours at the constant rotation speed at the temperature of 58 ℃, finishing the reaction, carrying out vacuum filtration, washing a filter cake for 3-5 times by using absolute ethyl alcohol, drying for 24 hours at the temperature of 40-50 ℃ in a vacuum drying box, taking out, grinding and sieving by using a 400-mesh sieve to obtain the modified graphene oxide.
5. The flame-retardant and corrosion-resistant rubber material according to claim 4, wherein the graphene dispersion, aniline and 5-aminosalicylic acid are used in a ratio of 30-50mL in step S21: 1mL of: 1g of a compound; in the step S22, the reinforcing agent is ammonium persulfate and sulfuric acid according to the dosage ratio of 0.017 mol: 50mL, wherein the dosage ratio of the mixture B, the initiator solution and the reinforcing agent is 100 mL: 40-50mL and 50 mL.
6. The flame-retardant and corrosion-resistant rubber material as claimed in claim 1, wherein the vulcanizing agent is one or more of 2, 4-dichlorobenzoyl peroxide, 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane, benzoyl peroxide and diisophenylpropyl peroxide.
7. The flame-retardant corrosion-resistant rubber material according to claim 1, wherein the antioxidant is one or two of N-phenyl-alpha-aniline and antioxidant 4020 which are mixed in any proportion.
8. The flame-retardant and corrosion-resistant rubber material according to claim 1, wherein the accelerator is one or more of thiuram accelerators, thiazole accelerators and sulfenamide accelerators mixed in any proportion.
9. The flame-retardant corrosion-resistant rubber material according to claim 1, comprising the following steps:
firstly, placing natural rubber into a 70 ℃ oven for baking for 12 hours, then cutting the natural rubber into strips, controlling the initial temperature of an internal mixer to be 80 ℃, controlling the rotating speed of a rotor to be 60r/min, putting a natural rubber strip and chloroprene rubber into the internal mixer, mixing for 20min, sequentially adding composite fibers, zinc oxide, modified graphene oxide and polystyrene into the internal mixer, continuously mixing for 30min, transferring the mixture to an open mill, adding a vulcanizing agent, stearic acid, an anti-aging agent, paraffin and an accelerator, and mixing for 30-50min to obtain a rubber compound;
and secondly, transferring the rubber compound obtained in the first step to a vulcanizing machine for molding, setting the pressure to be 10-12MPa, the temperature to be 150-180 ℃, the vulcanizing time to be 15-20min, and finally trimming and cutting to obtain the flame-retardant corrosion-resistant rubber material.
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