CN113583355A - Rubber material for one-to-two vulcanization production line and preparation method thereof - Google Patents
Rubber material for one-to-two vulcanization production line and preparation method thereof Download PDFInfo
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- CN113583355A CN113583355A CN202110875911.9A CN202110875911A CN113583355A CN 113583355 A CN113583355 A CN 113583355A CN 202110875911 A CN202110875911 A CN 202110875911A CN 113583355 A CN113583355 A CN 113583355A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
- C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
- H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
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- 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
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3009—Sulfides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
Abstract
The invention relates to the technical field of rubber for cables, in particular to a rubber material for a one-to-two vulcanization production line and a preparation method thereof, wherein the rubber material comprises the following raw materials: the ethylene propylene diene monomer comprises ethylene propylene diene monomer, a composite filler, a dispersing agent and a flame retardant, and comprises the following raw materials in parts by weight: 65-90 parts of ethylene propylene diene monomer, 5-15 parts of composite filler, 1-3 parts of dispersant and 0.5-2 parts of flame retardant. The invention aims to enable the cable to be vulcanized quickly in the vulcanization process, avoid the mutual friction and collision between the cable and between the cable and a production line from influencing the insulation performance and appearance of the cable, and enable the cable to have excellent heat resistance, aging resistance and flame retardance.
Description
Technical Field
The invention relates to the technical field of rubber for cables, in particular to a rubber material for a one-to-two vulcanization production line and a preparation method thereof.
Background
With the continuous development of industry, the application of power cables is also continuously expanded, and meanwhile, the requirements on the cables are more and more, higher and higher, so that the cables can adapt to various application environments.
At present, BV2.5 civil cables produced in the cable industry generally adopt a production line of a high-speed extruder of 80 models, and the maximum production and extrusion speed of the production and extrusion line reaches about 230 m/min, which is the highest extrusion speed and yield in the industry. The wire and cable processing production line mainly comprises the following devices: pay off rack, magnetic tension machine, cross powder case, rubber extruder, go up sealing device, vulcanize the pipeline, sealing device, belted tractor, cooling trough, vertical accumulator, power frequency spark machine, take-up etc. down, conventional rubber cable vulcanizes the production line and is "one" mode, promptly: one production line can only produce one cable at a time, so that the production efficiency is lower, and in a 'one-to-two' mode, one production line can produce two cables at a time, so that the production efficiency is greatly improved, and the enterprise cost is saved. However, when the production of one-to-two is carried out, the common rubber material cannot adapt to the production mode of one-to-two, so that in the vulcanization process of the cable, due to the fact that the vulcanization speed of the common rubber material is low, mutual friction between two cables and between the cable and a production line is easily caused, the appearance shape of the cable is influenced, the thickness of an insulating layer of the cable is also influenced, and the insulating property of the cable is further influenced.
Disclosure of Invention
In view of the above, the present invention provides a rubber material for a one-to-two vulcanization production line and a preparation method thereof, so that a cable can be vulcanized quickly in a vulcanization process, mutual friction and collision between the cable and the production line and between the cable and the production line are avoided, the insulation performance and appearance of the cable are not affected, and the cable has excellent heat resistance, aging resistance and flame retardance.
The invention solves the technical problems by the following technical means:
a rubber material for a one-to-two vulcanization production line comprises the following raw materials: ethylene propylene diene monomer, composite filler, dispersant and flame retardant.
Further, the rubber material comprises the following raw materials in parts by weight: 65-90 parts of ethylene propylene diene monomer, 5-15 parts of composite filler, 1-3 parts of dispersant and 0.5-2 parts of flame retardant.
Further, the rubber material comprises the following raw materials in parts by weight: 80 parts of ethylene propylene diene monomer, 10 parts of composite filler, 2 parts of dispersant and 1.5 parts of flame retardant.
Further, the ethylene propylene diene monomer rubber comprises any two or three of ethylene propylene diene monomer rubber 4045, ethylene propylene diene monomer rubber 4725P and ethylene propylene diene monomer rubber 4745P, the dispersing agent is a mixture of stearic acid amine and higher alcohol, and the flame retardant is trichlorobromomethane.
Ethylene-propylene-diene monomer is a copolymer of ethylene, propylene and a small amount of non-conjugated diene, is one of ethylene-propylene rubbers, is represented by EPDM (ethylene-propylene-diene monomer), and has excellent aging resistance such as ozone resistance, heat resistance, weather resistance and the like and excellent vulcanization characteristic because the main chain of the ethylene-propylene-diene monomer is composed of chemically stable saturated hydrocarbon and only contains unsaturated double bonds in side chains. The ethylene propylene diene monomer 4045 has good aging resistance and vulcanization performance, and also has good fluidity and plasticity, the ethylene propylene diene monomer 4725P has good aging resistance and vulcanization performance, and also has good stability, and the ethylene propylene diene monomer 4045 and the ethylene propylene diene monomer 4725P are used as base materials of cable insulation materials, so that the cable insulation layer has good aging resistance and vulcanization performance, and also has good processing performance.
The mixture of the amine stearate and the higher alcohol is used as a dispersing agent, so that the lubricating property and the thermal stability of the ethylene propylene diene monomer can be improved. The trichlorobromomethane is used as a reactive flame retardant, and the trichlorobromomethane and the ethylene propylene diene monomer are crosslinked, so that the ethylene propylene diene monomer polymer contains flame retardant components, the trichlorobromomethane has small influence on the service performance of the ethylene propylene diene monomer, the flame retardance is durable, and the cable has good flame retardant property.
Further, the preparation of the composite filler comprises the following steps: s1: passivating titanium dioxide: placing titanium dioxide powder in a placing frame, wherein the placing frame is provided with small holes, the diameter of each small hole is smaller than the particle size of titanium dioxide, placing the placing frame at the anode of an electrolyte, a stirring device is arranged in the placing frame, nano copper sulfide particles are added into the electrolyte, the electrolyte is a sodium chloride solution, depositing the nano copper sulfide particles on the titanium dioxide particles through direct electrophoresis, and washing and drying to obtain titanium dioxide passivated by copper sulfide;
s2: preparation of the composite filler: and (3) placing the titanium dioxide prepared in the step S1 in an ethyl 3, 3-di (tert-amyl peroxy) butyrate solution, heating in a water bath at the temperature of 30-37 ℃ for 5-12H, adding a silane coupling agent in the water bath heating process, and continuously stirring to prepare the pasty composite filler.
The titanium dioxide serving as the metal oxide has good heat-conducting property, good thermal stability and ultraviolet light shielding property, and can be used as a filler to increase the heat-conducting property of the ethylene propylene diene monomer rubber and synergistically enhance the aging resistance of the ethylene propylene diene monomer rubber. The copper sulfide fully passivates titanium dioxide particles in a mode of electrophoretic deposition matched with stirring, so that when titanium dioxide is compounded with ethyl 3, 3-di (tert-amyl peroxy) butyrate, the ethyl 3, 3-di (tert-amyl peroxy) butyrate is not directly decomposed. The 3, 3-di (tert-amyl peroxy) ethyl butyrate is used as a vulcanizing agent, and the vulcanizing agent can be fully dispersed in the ethylene propylene diene monomer rubber material by compounding with titanium dioxide, so that the vulcanization speed of the ethylene propylene diene monomer rubber is higher and more sufficient, and the friction of an insulating layer is avoided.
Further, during the direct-current electrophoretic deposition, an intermittent electrophoretic deposition method is adopted, and the voltages of the intermittent electrophoretic deposition method are respectively as follows: 15V/25V/35V, and the current is 15mA/25mA/35mA respectively.
The copper sulfide is very stable and is difficult to dissolve in a sodium chloride solution, the copper sulfide particles can be fully deposited on the titanium dioxide particles through intermittent pressurization, and the copper sulfide particles and the titanium dioxide are combined more tightly and cannot fall off easily due to the intermittent pressurization.
The invention also discloses a preparation method of the rubber material for the one-to-two vulcanization production line, which comprises the following steps:
a1: chlorination of ethylene propylene diene monomer: putting ethylene propylene diene monomer 4045 and ethylene propylene diene monomer 4725P into a carbon tetrachloride solution, continuously stirring for 2-8H at 40-50 ℃, stirring to completely dissolve the ethylene propylene diene monomer 4045 and the ethylene propylene diene monomer 4725P, gradually adding an initiator in the stirring process, continuously introducing chlorine after the initiator reacts for 0.5-1H, stopping introducing the chlorine after the reaction is finished, cooling to normal temperature, adding methanol into the solution to preliminarily precipitate a mixed product, adding a methanol-toluene mixed solution, continuously precipitating for 2-3 times, completely precipitating the mixed product, removing the solution after the mixed product is completely precipitated, washing with deionized water, and drying to obtain a chlorinated ethylene propylene diene monomer mixture;
a2: mixing: placing the chlorinated ethylene propylene diene monomer prepared in the step A1 on an open mill, mixing for 1min, adding the composite filler and the dispersant, mixing for 3-5min, adding the flame retardant, and mixing for 2-3 min;
a3: aging: and aging the mixed ethylene propylene diene monomer rubber for 10-24H at the temperature of 8-15 ℃ to obtain the rubber material after aging.
The ethylene propylene diene monomer is chlorinated firstly, the chlorinated ethylene propylene diene monomer has higher vulcanization speed, and then the composite filler, the dispersing agent, the flame retardant and the chlorinated ethylene propylene diene monomer are mixed, so that the composite filler and the flame retardant can be fully dispersed in the ethylene propylene diene monomer, the chlorinated ethylene propylene diene monomer can act with the vulcanizing agent in a synergistic manner, and the ethylene propylene diene monomer is matched with the rapid heat conduction of titanium dioxide, so that the ethylene propylene diene monomer can be vulcanized rapidly, compared with a common rubber material, the vulcanization speed can be improved by 2-3.5 times at the same temperature, thereby avoiding the friction and collision deformation of an insulating layer of a one-to-two cable in the vulcanization process, and reducing the influence on the performance of the insulating layer. Through aging, the composite filler, the flame retardant and the ethylene propylene diene monomer are combined more fully, and meanwhile, the decomposition of organic peroxide in the composite filler caused by mixing is avoided.
In the step a1, the initiator is any one of azobisisoheptonitrile, tert-butyl hydroperoxide/sodium metabisulfite, cumene hydroperoxide, tert-butyl hydroperoxide, and di-tert-butyl peroxide.
By adding the initiator, the ethylene propylene diene monomer 4045 and the ethylene propylene diene monomer 4725P can be fully chlorinated.
Further, in the step a1, the drying conditions are as follows: baking at 60-70 deg.C for 1-2.5H.
By limiting the baking temperature, the direct vulcanization of the ethylene propylene diene monomer rubber caused by overhigh baking temperature is avoided, and the dead rubber is formed.
The invention has the beneficial effects that: through mixing the ethylene propylene diene monomer 4045 and the ethylene propylene diene monomer 4725P, chlorinating, compounding titanium dioxide and organic peroxide, and adding the filler into the chlorinated ethylene propylene diene monomer after compounding, the chlorinated ethylene propylene diene monomer and the composite filler can act synergistically during vulcanization of the ethylene propylene diene monomer, so that the vulcanization speed of the ethylene propylene diene monomer is increased, compared with a common rubber material, the vulcanization speed can be increased by 2-3.5 times at the same temperature, friction and collision of an insulating layer of a one-out-two cable in the vulcanization process are avoided, and the influence on the performance of the insulating layer is reduced; and the insulating layer has good aging resistance and flame retardant property, so that the service life of the cable is prolonged.
Detailed Description
The present invention will be described in detail with reference to specific examples below:
example 1 preparation of composite Filler
S1: passivating titanium dioxide: placing 10 parts by mass of titanium dioxide powder in a placing frame, wherein the placing frame is provided with small holes, the diameter of each small hole is smaller than the particle size of titanium dioxide, the placing frame is a plastic product, the adsorption of copper sulfide particles is reduced, an electrolyte is a sodium chloride solution, the placing frame is placed at an anode of the electrolyte, a stirring device is arranged in the placing frame, stirring is carried out at the speed of 75r/min, 12 parts by mass of nano copper sulfide particles are added into the electrolyte, direct current is introduced intermittently, the voltage of the direct current is 15V/25V/35V respectively, the current is 15mA/25mA/35mA respectively, the nano copper sulfide particles are deposited on the titanium dioxide particles through direct electrophoresis deposition, after the electrophoresis deposition, the titanium dioxide in the placing frame is taken out, deionized water is soaked for 30min, the titanium dioxide is washed again after soaking, and is placed in a drying device after the washing is finished, baking for 10H at 100 ℃, and obtaining titanium dioxide passivated by copper sulfide after baking;
s2: preparation of the composite filler: and (3) putting 8 parts by mass of passivated titanium dioxide into 12 parts by mass of ethyl 3, 3-di (tert-amyl peroxy) butyrate solution, heating in a water bath at 30 ℃ for 12H, adding 2.3 parts by mass of silane coupling agent in the heating process in the water bath, and continuously stirring at the rotating speed of 40r/min until the whole solution is pasty to obtain the pasty composite filler.
Example 2 preparation of composite Filler
S1: passivating titanium dioxide: placing 20 parts by mass of titanium dioxide powder in a placing frame, wherein the placing frame is provided with small holes, the diameter of each small hole is smaller than the particle size of titanium dioxide, the placing frame is a plastic product, the adsorption of copper sulfide particles is reduced, an electrolyte is a sodium chloride solution, the placing frame is placed at an anode of the electrolyte, a stirring device is arranged in the placing frame, stirring is carried out at the speed of 100r/min, 26 parts by mass of nano copper sulfide particles are added into the electrolyte, direct current is introduced intermittently, the voltage of the direct current is 15V/25V/35V respectively, the current is 15mA/25mA/35mA respectively, the nano copper sulfide particles are deposited on the titanium dioxide particles through direct electrophoresis deposition, after the electrophoresis deposition, the titanium dioxide in the placing frame is taken out, deionized water is soaked for 45min, the titanium dioxide is washed again after soaking, and is placed in a drying device after the washing is finished, baking for 8H at 110 ℃, and obtaining titanium dioxide passivated by copper sulfide after baking;
s2: preparation of the composite filler: and (3) putting 10 parts by mass of passivated titanium dioxide into 16 parts by mass of ethyl 3, 3-di (tert-amyl peroxy) butyrate solution, heating in a water bath at 34 ℃ for 8H, adding 4.7 parts by mass of silane coupling agent in the heating process in the water bath, and continuously stirring at the rotating speed of 50r/min until the whole solution is pasty to obtain the pasty composite filler.
Example 3 preparation of composite Filler
S1: passivating titanium dioxide: placing 30 parts by mass of titanium dioxide powder in a placing frame, wherein the placing frame is provided with small holes, the diameter of each small hole is smaller than the particle size of titanium dioxide, the placing frame is a plastic product, the adsorption of copper sulfide particles is reduced, an electrolyte is a sodium chloride solution, the placing frame is placed at an anode of the electrolyte, a stirring device is arranged in the placing frame, the stirring is carried out at the speed of 120r/min, 40 parts by mass of nano copper sulfide particles are added into the electrolyte, direct current is introduced intermittently, the voltage of the direct current is 15V/25V/35V respectively, the current is 15mA/25mA/35mA respectively, the nano copper sulfide particles are deposited on the titanium dioxide particles through direct electrophoresis deposition, after the electrophoresis deposition, the titanium dioxide in the placing frame is taken out, deionized water is soaked for 60min, the soaking is carried out, the rinsing is carried out again, the washing is carried out, and the titanium dioxide is placed in a drying device after the washing, baking for 5H at 120 ℃, and obtaining titanium dioxide passivated by copper sulfide after baking;
s2: preparation of the composite filler: taking 15 parts by mass of passivated titanium dioxide, placing the passivated titanium dioxide in 23 parts by mass of ethyl 3, 3-di (tert-amyl peroxy) butyrate solution, heating the solution in a water bath for 5H at 37 ℃, adding 6.4 parts by mass of silane coupling agent in the heating process in the water bath, and continuously stirring the solution at the rotating speed of 60r/min until the whole solution is pasty, thereby obtaining the pasty composite filler.
Example 4 preparation of rubber Material
A1: chlorination of ethylene propylene diene monomer: putting 5 parts by mass of ethylene propylene diene monomer 4045 and 5 parts by mass of ethylene propylene diene monomer 4725P into 20 parts by mass of carbon tetrachloride solution, continuously stirring for 8H at 40 ℃, stirring the ethylene propylene diene monomer 4045 and the ethylene propylene diene monomer 4725P until the ethylene propylene diene monomer 4725P is completely dissolved, gradually adding 1.5 parts by mass of azobisisoheptonitrile during stirring, continuously introducing chlorine after the azobisisoheptonitrile reacts for 0.5H, introducing the chlorine at the speed of 20ml/min, stopping introducing the chlorine after the chlorine reaction is finished, cooling to normal temperature, adding 50 parts by mass of methanol into the solution to preliminarily precipitate a mixed product, adding 50 parts by mass of methanol-toluene mixed solution, continuously precipitating for 2-3 times, completely precipitating the mixed product, removing the solution after the mixed product is completely precipitated, washing with deionized water, drying for 8H at 50 ℃, obtaining a chlorinated ethylene propylene diene monomer mixture;
a2: mixing: taking 65 parts by mass of the chlorinated ethylene propylene diene monomer prepared in the step A1, placing the chlorinated ethylene propylene diene monomer on an open mill, mixing for 1min, adding 5 parts by mass of composite filler and 1 part by mass of dispersant, mixing for 3-5min, adding 0.5 part by mass of flame retardant, and mixing for 2-3 min;
a3: aging: and aging the mixed ethylene propylene diene monomer rubber for 10 hours at the temperature of 8 ℃ to obtain the rubber material after aging.
Example 5 preparation of rubber Material II
A1: chlorination of ethylene propylene diene monomer: putting 10 parts by mass of ethylene propylene diene monomer 4045 and 10 parts by mass of ethylene propylene diene monomer 4725P into 40 parts by mass of carbon tetrachloride solution, continuously stirring for 5H at 45 ℃, stirring the ethylene propylene diene monomer 4045 and the ethylene propylene diene monomer 4725P until the ethylene propylene diene monomer 4725P is completely dissolved, gradually adding 2.5 parts by mass of azobisisoheptonitrile during stirring, continuously introducing chlorine after the azobisisoheptonitrile reacts for 45min, introducing the chlorine at the speed of 20ml/min, stopping introducing the chlorine after the chlorine reaction is finished, cooling to normal temperature, adding 70 parts by mass of methanol into the solution to preliminarily precipitate a mixed product, adding 70 parts by mass of methanol-toluene mixed solution, continuously precipitating for 2-3 times, completely precipitating the mixed product, removing the solution after the mixed product is completely precipitated, washing with deionized water, drying for 6H at 55 ℃, obtaining a chlorinated ethylene propylene diene monomer mixture;
a2: mixing: taking 75 parts by mass of the chlorinated ethylene propylene diene monomer prepared in the step A1, placing the chlorinated ethylene propylene diene monomer on an open mill, mixing for 1min, adding 10 parts by mass of composite filler and 2 parts by mass of dispersant, mixing for 3-5min, adding 1.5 parts by mass of flame retardant, and mixing for 2-3 min;
a3: aging: and aging the mixed ethylene propylene diene monomer rubber for 15H at the temperature of 12 ℃ to obtain the rubber material after aging.
Example 6 preparation of rubber Material III
A1: chlorination of ethylene propylene diene monomer: putting 15 parts by mass of ethylene propylene diene monomer 4045 and 15 parts by mass of ethylene propylene diene monomer 4725P into 60 parts by mass of carbon tetrachloride solution, continuously stirring for 2H at 50 ℃, stirring the ethylene propylene diene monomer 4045 and the ethylene propylene diene monomer 4725P until the ethylene propylene diene monomer 4725P is completely dissolved, gradually adding 4 parts by mass of azobisisoheptonitrile during stirring, continuously introducing chlorine after the azobisisoheptonitrile reacts for 60min, stopping introducing the chlorine at the speed of 20ml/min, cooling to normal temperature after the chlorine reaction is finished, adding 100 parts by mass of methanol into the solution to primarily precipitate a mixed product, adding 100 parts by mass of methanol-toluene mixed solution, continuously precipitating for 2-3 times, completely precipitating the mixed product, removing the solution after the mixed product is completely precipitated, washing with deionized water, drying for 2.5H at 60 ℃, obtaining a chlorinated ethylene propylene diene monomer mixture;
a2: mixing: taking 90 parts by mass of the chlorinated ethylene propylene diene monomer prepared in the step A1, placing the chlorinated ethylene propylene diene monomer on an open mill, mixing for 1min, adding 15 parts by mass of composite filler and 3 parts by mass of dispersant, mixing for 3-5min, adding 2 parts by mass of flame retardant, and mixing for 2-3 min;
a3: aging: and aging the mixed ethylene propylene diene monomer rubber for 10 hours at 15 ℃ to obtain the rubber material after aging.
Example 7 (comparative example one), preparation of rubber Material four
A1: chlorination of ethylene propylene diene monomer: putting 10 parts by mass of ethylene propylene diene monomer 4045 and 10 parts by mass of ethylene propylene diene monomer 4725P into 40 parts by mass of carbon tetrachloride solution, continuously stirring for 5H at 45 ℃, stirring the ethylene propylene diene monomer 4045 and the ethylene propylene diene monomer 4725P until the ethylene propylene diene monomer 4725P is completely dissolved, gradually adding 2.5 parts by mass of azobisisoheptonitrile during stirring, continuously introducing chlorine after the azobisisoheptonitrile reacts for 45min, introducing the chlorine at the speed of 20ml/min, stopping introducing the chlorine after the chlorine reaction is finished, cooling to normal temperature, adding 70 parts by mass of methanol into the solution to preliminarily precipitate a mixed product, adding 70 parts by mass of methanol-toluene mixed solution, continuously precipitating for 2-3 times, completely precipitating the mixed product, removing the solution after the mixed product is completely precipitated, washing with deionized water, drying for 6H at 55 ℃, obtaining a chlorinated ethylene propylene diene monomer mixture;
a2: mixing: taking 75 parts by mass of the chlorinated ethylene propylene diene monomer prepared in the step A1, placing the chlorinated ethylene propylene diene monomer on an open mill, mixing for 1min, then adding 10 parts by mass of titanium dioxide and 2 parts by mass of dispersing agent, mixing for 3-5min, adding 1.5 parts by mass of flame retardant, and mixing for 2-3 min;
a3: aging: and aging the mixed ethylene propylene diene monomer rubber for 15H at the temperature of 12 ℃ to obtain the rubber material after aging.
Example 8 (comparative example two), preparation of rubber Material five
A1: chlorination of ethylene propylene diene monomer: 10 parts by mass of ethylene propylene diene monomer 4745P is put into 40 parts by mass of carbon tetrachloride solution, continuously stirring for 5H at 45 ℃, stirring the ethylene propylene diene monomer 4045 and the ethylene propylene diene monomer 4725P until the ethylene propylene diene monomer 4045 and the ethylene propylene diene monomer 4725P are completely dissolved, 2.5 parts by mass of azobisisoheptonitrile is gradually added in the stirring process, chlorine is continuously introduced after the azobisisoheptonitrile reacts for 45min, the chlorine is introduced at the speed of 20ml/min, the chlorine introduction is stopped after the chlorine reaction is finished, the chlorine is cooled to the normal temperature, adding 70 parts by mass of methanol into the solution to precipitate a mixed product primarily, adding 70 parts by mass of methanol-toluene mixed solution, continuing to precipitate for 2-3 times, completely precipitating the mixed product, removing the solution, washing with deionized water, and drying for 6H at 55 ℃ to obtain a chlorinated ethylene propylene diene monomer mixture;
a2: mixing: taking 75 parts by mass of the chlorinated ethylene propylene diene monomer prepared in the step A1, placing the chlorinated ethylene propylene diene monomer on an open mill, mixing for 1min, adding 10 parts by mass of composite filler and 2 parts by mass of dispersant, mixing for 3-5min, adding 1.5 parts by mass of flame retardant, and mixing for 2-3 min;
a3: aging: and aging the mixed ethylene propylene diene monomer rubber for 15H at the temperature of 12 ℃ to obtain the rubber material after aging.
The rubber materials prepared in examples 4 to 8 were tested for Mooney viscosity, elongation at break, tensile strength, aging resistance, flame retardancy and vulcanization rate, and the following test results were obtained:
| item | Elongation at Break (%) | Tensile Strength (MPa) | Ageing resistance (30 days, expressed as colour difference) | Flame retardant rating | Vulcanization speed (180 ℃/S) |
| Example 4 | 350 | 15 | 3.81 | V-2 | 56 |
| Example 5 | 375 | 18 | 3.52 | V-2 | 48 |
| Example 6 | 367 | 16 | 3.66 | V-2 | 51 |
| Example 7 | 362 | 16 | 4.35 | V-2 | 89 |
| Example 8 | 343 | 14 | 6.85 | V-2 | 114 |
As can be seen from the data in the table, in examples 4-6, the elongation at break, tensile strength, aging resistance, flame retardant property and vulcanization speed of the rubber material prepared in example 5 are all superior to those of examples 4 and 6, which shows that the rubber material prepared by using the ethylene propylene diene monomer 4045, the ethylene propylene diene monomer 4725P, the composite filler and the flame retardant together has good elongation at break, tensile strength, aging resistance, flame retardant property and vulcanization speed, and is more suitable for the one-to-two vulcanization production line.
By comparing the data of example 5 with the data of example 7, it can be shown that the elongation at break and the tensile strength of the rubber material are reduced, and the vulcanization speed is reduced, which shows that the ethylene propylene diene monomer and the composite filler play a synergistic role in vulcanization speed, the vulcanization speed of the ethylene propylene diene monomer can be accelerated, and simultaneously, the elongation at break and the tensile strength can be synergistically enhanced.
By comparing the data of example 5 with the data of example 8, it can be shown that the elongation at break, tensile strength, aging resistance, flame retardant property and vulcanization speed of the rubber material using the ethylene propylene diene monomer 4745P as the base material are reduced to different degrees, which indicates that the mixed use of the ethylene propylene diene monomer 4045 and the ethylene propylene diene monomer 4725P can play a synergistic role in increasing the vulcanization speed.
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the invention as defined in the appended claims. The techniques, shapes, and configurations not described in detail in the present invention are all known techniques.
Claims (9)
1. The rubber material for the one-to-two vulcanization production line is characterized by comprising the following raw materials: ethylene propylene diene monomer, composite filler, dispersant and flame retardant.
2. The rubber material for the one-to-two vulcanization production line according to claim 1, characterized in that the rubber material comprises the following raw materials in parts by weight: 65-90 parts of ethylene propylene diene monomer, 5-15 parts of composite filler, 1-3 parts of dispersant and 0.5-2 parts of flame retardant.
3. The rubber material for the one-to-two vulcanization production line according to claim 2, characterized by comprising the following raw materials in parts by weight: 80 parts of ethylene propylene diene monomer, 10 parts of composite filler, 2 parts of dispersant and 1.5 parts of flame retardant.
4. The rubber material for the one-out-two vulcanization production line according to claim 3, wherein the ethylene propylene diene monomer rubber comprises any two or three of ethylene propylene diene monomer rubber 4045, ethylene propylene diene monomer rubber 4725P and ethylene propylene diene monomer rubber 4745P, the dispersing agent is a mixture of amine stearate and higher alcohol, and the flame retardant is trichlorobromomethane.
5. The rubber material for the one-out-two vulcanization production line according to claim 4, characterized in that the preparation of the composite filler comprises the following steps: s1: passivating titanium dioxide: placing titanium dioxide powder in a placing frame, wherein the placing frame is provided with small holes, the diameter of each small hole is smaller than the particle size of titanium dioxide, placing the placing frame at the anode of an electrolyte, a stirring device is arranged in the placing frame, nano copper sulfide particles are added into the electrolyte, the electrolyte is a sodium chloride solution, depositing the nano copper sulfide particles on the titanium dioxide particles through direct electrophoresis, and washing and drying to obtain titanium dioxide passivated by copper sulfide;
s2: preparation of the composite filler: and (3) placing the titanium dioxide prepared in the step S1 in an ethyl 3, 3-di (tert-amyl peroxy) butyrate solution, heating in a water bath at the temperature of 30-37 ℃ for 5-12H, adding a silane coupling agent in the water bath heating process, and continuously stirring to prepare the pasty composite filler.
6. The rubber material for the one-to-two vulcanization production line according to claim 5, wherein the direct-flow electrophoretic deposition is performed by an intermittent electrophoretic deposition method, and the voltages of the intermittent electrophoretic deposition method are respectively: 15V/25V/35V, and the current is 15mA/25mA/35mA respectively.
7. A method for preparing a rubber material for a one-out-two vulcanization production line according to any one of claims 1 to 6, characterized by comprising the steps of: a1: chlorination of ethylene propylene diene monomer: putting ethylene propylene diene monomer 4045 and ethylene propylene diene monomer 4725P into a carbon tetrachloride solution, continuously stirring for 2-8H at 40-50 ℃, stirring to completely dissolve the ethylene propylene diene monomer 4045 and the ethylene propylene diene monomer 4725P, gradually adding an initiator in the stirring process, continuously introducing chlorine after the initiator reacts for 0.5-1H, stopping introducing the chlorine after the reaction is finished, cooling to normal temperature, adding methanol into the solution to preliminarily precipitate a mixed product, adding a methanol-toluene mixed solution, continuously precipitating for 2-3 times, completely precipitating the mixed product, removing the solution after the mixed product is completely precipitated, washing with deionized water, and drying to obtain a chlorinated ethylene propylene diene monomer mixture;
a2: mixing: placing the chlorinated ethylene propylene diene monomer prepared in the step A1 on an open mill, mixing for 1min, adding the composite filler and the dispersant, mixing for 3-5min, adding the flame retardant, and mixing for 2-3 min;
a3: aging: and aging the mixed ethylene propylene diene monomer rubber for 10-24H at the temperature of 8-15 ℃ to obtain the rubber material after aging.
8. The method for producing a rubber material for a "one-out-two" vulcanization line according to claim 7, wherein in the step A1, the initiator is any one of azobisisoheptonitrile, t-butyl hydroperoxide/sodium metabisulfite, cumene hydroperoxide, t-butyl hydroperoxide, and di-t-butyl peroxide.
9. The method for preparing a rubber material for a one-out-two vulcanization production line according to claim 8, wherein in the step A1, the drying conditions are as follows: baking at 60-70 deg.C for 1-2.5H.
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