CN112812415A - Heat-resistant ethylene-vinyl acetate rubber cable material and preparation method thereof - Google Patents
Heat-resistant ethylene-vinyl acetate rubber cable material and preparation method thereof Download PDFInfo
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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
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/246—Intercrosslinking of at least two polymers
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/28—Treatment by wave energy or particle radiation
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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
- H01B3/28—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances natural or synthetic rubbers
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- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
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- C—CHEMISTRY; METALLURGY
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- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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- 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
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- 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
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Abstract
The invention discloses a preparation method of an ethylene-vinyl acetate rubber heat-resistant cable material, which comprises the following steps: sequentially adding the components according to the formula amount, and uniformly dispersing under the conditions of assisting ultrasonic waves and microwaves under the closed mixing condition to obtain a mixture A; adding the cross-linking agent under the conditions of ultrasonic waves and microwaves under the open mixing condition, uniformly turning, and rolling to obtain a mixture B; under the extrusion vulcanization condition, the mixture B is extruded, vulcanized and crosslinked to obtain the ethylene-vinyl acetate rubber heat-resistant cable material; also discloses an ethylene-vinyl acetate rubber heat-resistant cable material. According to the invention, through the optimization of the selection and content of each component, the improvement of the preparation process and the synergistic cooperation effect, the cable material with high temperature resistance, aging resistance, high strength and high toughness is manufactured and is used for coating the outer periphery of the wire, so that the power line meets the requirements of heat resistance at 110 ℃ and aging resistance.
Description
Technical Field
The invention relates to the technical field of cable production, in particular to an ethylene-vinyl acetate rubber heat-resistant cable material and a preparation method thereof.
Background
Along with the popularization of household appliances, the development of the household appliance industry drives the rapid development of the special wire industry, and more household appliances such as kitchen appliances can generate heat, so that the power line of the household appliance needs to have better heat resistance, and the requirement of the novel wire type in the industry is further promoted to be more vigorous. At present, the domestic power line standard only has power lines for common household appliances, and the temperature resistance can not meet the daily requirements of the household appliances. The temperature resistance requirement of the current household appliance standard on a power line is improved to 80 ℃ from the original common 60 ℃, and some household appliances even require 105 ℃. Therefore, the cable material for producing the rubber wire is required to have special performance requirements of high strength, high toughness, high temperature resistance and the like. But the development of the special power line insulating material at home and abroad at present is not enough, and the selectivity of the special material for enhancing the performance requirements of all aspects is not enough.
Therefore, how to optimize the preparation conditions and formula content of the cable material and further obtain the cable material with the characteristics of high temperature resistance, aging resistance, high strength, high toughness and the like becomes a main technical problem at present.
Disclosure of Invention
In order to overcome the technical problems, the invention discloses a preparation method of an ethylene-vinyl acetate rubber heat-resistant cable material; also discloses an ethylene-vinyl acetate rubber heat-resistant cable material.
The technical scheme adopted by the invention for realizing the purpose is as follows:
a preparation method of an ethylene-vinyl acetate rubber heat-resistant cable material comprises the following steps:
step 1, sequentially adding the components according to the formula amount, and uniformly dispersing under the conditions of ultrasonic waves and microwaves under the closed mixing condition to obtain a mixture A;
step 2, adding the cross-linking agent into the mixture A under the open mixing condition with the assistance of ultrasonic waves and microwaves, turning uniformly, and rolling to obtain a mixture B;
and 3, extruding, vulcanizing and crosslinking the mixture B under the extrusion vulcanization condition by assisting ultrasonic waves and microwaves to obtain the ethylene-vinyl acetate rubber heat-resistant cable material.
The preparation method of the ethylene-vinyl acetate rubber heat-resistant cable material comprises the following steps of: sequentially adding a filling reinforcing agent, a crosslinking assistant, a plasticizer, an anti-aging agent, a coloring agent, a processing assistant, ethylene propylene rubber and ethylene-vinyl acetate rubber.
In the step 3, the extrusion vulcanization condition is a two-step reaction, wherein saturated steam is adopted in the first vulcanization step, and constant-temperature air-blast oil seal is adopted in the second vulcanization step;
the first vulcanization step conditions were: vulcanizing pressure is 1.7-2 MPa, time is 1-6 min, an extruder comprising a three-section type 100m vulcanizing pipeline is adopted, the temperature of a machine body and a machine head of the extruder is 50 ℃ and 53 ℃, the temperature of a first section is 200 ℃, the temperature of a second section is 210-220 ℃, and the temperature of a third section is 230 ℃;
the second sulfurization step conditions are as follows: the temperature is 130-150 ℃, and the time is 1-1.5 h; the temperature is 180-220 ℃, and the time is 2.5-4 h.
The ethylene-vinyl acetate rubber heat-resistant cable material is prepared by the preparation method of the ethylene-vinyl acetate rubber heat-resistant cable material, and comprises the following components in parts by mass: 26-45 parts of a rubber base material, 25-40 parts of a filling reinforcing agent, 2-7 parts of a crosslinking composition, 3.5-12.5 parts of a function maintaining composition, 0-1 part of a coloring agent and 0-1 part of a processing aid.
The ethylene-vinyl acetate rubber heat-resistant cable material comprises the following components in parts by weight: 25-40 parts of ethylene-vinyl acetate rubber and 1-5 parts of ethylene-propylene rubber.
The ethylene-vinyl acetate rubber heat-resistant cable material comprises the following components in parts by weight: 1-3 parts of a crosslinking agent and 1-4 parts of a crosslinking assistant.
The ethylene-vinyl acetate rubber heat-resistant cable material comprises the following components in parts by weight: 2.5-6 parts of plasticizer, 0.5-5 parts of stabilizer and 0.5-1.5 parts of anti-aging agent.
The ethylene-vinyl acetate rubber heat-resistant cable material comprises the following components in percentage by mass, wherein the mass ratio of the plasticizer to the filling reinforcing agent is 1: 2-8, wherein the mass percent of the anti-aging agent to the crosslinking composition is 0.5-3%: 1.
the ethylene-vinyl acetate rubber heat-resistant cable material comprises 3-8% of the cross-linking composition and the rubber base material by mass: 1, the mass ratio of the cross-linking agent to the cross-linking auxiliary agent is 1: 1 to 2.
The ethylene-vinyl acetate rubber heat-resistant cable material comprises 0-10% of ethylene propylene rubber and a rubber base material by mass: 1.
the invention has the beneficial effects that:
(1) according to the invention, through the optimization of the selection and content of each component, the improvement of the preparation process and the synergistic cooperation effect, the cable material with high temperature resistance, aging resistance, high strength and high toughness is manufactured and used for coating the outer periphery of the wire, so that the power line meets the requirements of heat resistance at 110 ℃ and aging resistance, and the defects of small application range, low strength, poor cold resistance, poor durability, poor oxidation resistance and the like of the traditional cable material are improved;
(2) the mixing process conditions have great influence on the performance of the mixed cable material, and the method aims to improve the dispersion uniformity of each component in a rubber system, ensure the uniform dispersion of each component by controlling the feeding sequence, the closed mixing conditions, the open mixing conditions and the like, eliminate internal stress and ensure good mixing quality and high performance of products;
(3) various components are sequentially added to create a dispersion system with strong dispersion compatibility, and the crosslinking interaction between the ethylene propylene rubber and the ethylene-vinyl acetate rubber is enhanced under the action of the crosslinking composition by utilizing the chemical reaction between the ethylene propylene rubber and the ethylene-vinyl acetate rubber, so that the strong combination effect of the ethylene propylene rubber and the ethylene-vinyl acetate rubber is realized, and the comprehensive performance of the cable material is further optimized;
(4) proper ultrasonic waves and microwaves are supplemented in the preparation process, and due to the synergy of the ultrasonic waves and the microwaves, the rubber base material and the crosslinking composition are promoted to be fully copolymerized and crosslinked, so that the vulcanization effect and efficiency are further improved, and the comprehensive performance of the cable material is optimized;
(5) the two-step extrusion vulcanization condition is adopted, and peroxide is used as the crosslinking agent, so that the crosslinking degree and the uniformity of the crosslinking composition and the rubber base material are effectively controlled, the rubber system is promoted to be crosslinked mutually under different vulcanization environments, the vulcanization speed and the process adaptability of continuous production are improved, and the quality stability of products is improved;
(6) the ethylene propylene rubber with a specific ratio is adopted, so that the crosslinking polymerization degree and the tensile strength of the cable material are effectively promoted to a proper range, and the overall performance of the cable material is optimized; the ethylene-vinyl acetate rubber with the appropriate vinyl acetate content can improve the mixing and extrusion performance of the cable material, and can replace the traditional added flame retardant so as to meet the requirements of high flame retardance and heat resistance; secondly, the high ethylene content and the low Mooney viscosity of the ethylene propylene rubber effectively improve the vulcanization performance and the processing convenience of the cable material; the ethylene-vinyl acetate rubber is selected, the thermoplastic elastomer has high bond energy, and has the advantages of high temperature resistance, aging resistance, good elasticity, good flexibility and the like, and the ethylene-propylene rubber with low viscosity is matched, as the main chain of the ethylene-vinyl acetate rubber is composed of chemically stable saturated hydrocarbon, only unsaturated double bonds are contained in the side chain, the ethylene-propylene rubber has the properties of high temperature resistance, aging resistance and the like, under the action of the components such as the crosslinking composition and the like, the crosslinking performance between the ethylene-vinyl acetate rubber and the ethylene-propylene rubber is effectively promoted, the full vulcanization is ensured, and the synergistic effect of the ethylene-vinyl;
(7) the proper amount of the filling reinforcing agent can improve the voltage-resistant insulating property of the cable material, can also improve the high-temperature aging-resistant property and the high-temperature insulating property of the cable material, and has better reinforcing effect; the stabilizer is used for maintaining the crosslinking stability of the cable material in the vulcanization process and further optimizing the comprehensive performance of the cable material.
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to facilitate the understanding and appreciation of the technical solutions of the present invention, rather than to limit the invention thereto.
The invention discloses a preparation method of an ethylene-vinyl acetate rubber heat-resistant cable material, which comprises the following steps:
step 1, sequentially adding the components according to the formula amount, and uniformly dispersing under the conditions of ultrasonic waves and microwaves under the closed mixing condition to obtain a mixture A;
step 2, adding the cross-linking agent into the mixture A under the open mixing condition with the assistance of ultrasonic waves and microwaves, turning uniformly, and rolling to obtain a mixture B;
and 3, extruding, vulcanizing and crosslinking the mixture B under the extrusion vulcanization condition by assisting ultrasonic waves and microwaves to obtain the ethylene-vinyl acetate rubber heat-resistant cable material.
Preferably, the adding sequence of the components in the step 1 is as follows: sequentially adding a filling reinforcing agent, a crosslinking assistant, a plasticizer, an anti-aging agent, a coloring agent, a processing assistant, ethylene propylene rubber and ethylene-vinyl acetate rubber; various components are sequentially added to create a dispersion system with strong dispersion compatibility, and the crosslinking interaction between the ethylene propylene rubber and the ethylene-vinyl acetate rubber is enhanced under the action of a crosslinking agent and a crosslinking assistant by utilizing the chemical reaction between the ethylene propylene rubber and the ethylene-vinyl acetate rubber, so that the strong combination of the ethylene propylene rubber and the ethylene-vinyl acetate rubber is realized, and the comprehensive performance of the cable material is further optimized.
Preferably, the ethylene-vinyl acetate rubber heat-resistant cable material comprises the following components in parts by weight: 26-45 parts of a rubber base material, 25-40 parts of a filling reinforcing agent, 2-7 parts of a crosslinking composition, 3.5-12.5 parts of a function maintaining composition, 0-1 part of a coloring agent and 0-1 part of a processing aid.
Preferably, the rubber base material comprises the following components in parts by mass: 25-40 parts of ethylene-vinyl acetate rubber and 1-5 parts of ethylene-propylene rubber; the crosslinking composition comprises the following components in parts by mass: 1-3 parts of a crosslinking agent and 1-4 parts of a crosslinking assistant; the function maintaining composition comprises the following components in parts by weight: 2.5-6 parts of a plasticizer, 0.5-5 parts of a stabilizer and 0.5-1.5 parts of an anti-aging agent; the mass ratio of the plasticizer to the filling reinforcing agent is 1: 2-8, wherein the mass percent of the anti-aging agent to the crosslinking composition is 0.5-3%: 1.
preferably, in step 3, the extrusion vulcanization condition is a two-step reaction, wherein saturated steam is adopted in the first vulcanization step, and constant-temperature air-blast oil seal is adopted in the second vulcanization step;
the first vulcanization step conditions were: vulcanizing pressure is 1.7-2 MPa, time is 1-6 min, an extruder comprising a three-section type 100m vulcanizing pipeline is adopted, the temperature of a machine body and a machine head of the extruder is 50 ℃ and 53 ℃, the temperature of a first section is 200 ℃, the temperature of a second section is 210-220 ℃, and the temperature of a third section is 230 ℃;
the second sulfurization step conditions are as follows: the temperature is 130-150 ℃, and the time is 1-1.5 h; the temperature is 180-220 ℃, and the time is 2.5-4 h.
Preferably, the ultrasonic wave and microwave conditions are as follows: the ultrasonic wave with the power of 200W, the power of 100-300W and the frequency of 40-60 kHz stops intermittently for 20-40 s every 10s when the ultrasonic wave works; proper ultrasonic waves and microwaves are supplemented in the preparation process, and the ultrasonic waves and the microwaves are cooperated to promote the rubber base material and the crosslinking composition to be fully copolymerized and crosslinked, so that the vulcanization effect and efficiency are further improved.
Preferably, in step 1, the internal mixing conditions are as follows: controlling the temperature to be 30-110 ℃, controlling the rotating speed to be 40-60 r/min, banburying for 5-12 min, then heating to 50-170 ℃, banburying for 20-40 min, and maintaining the glue temperature to be 155-170 ℃.
Preferably, in step 2, the open mixing conditions are as follows: the roller temperature is 45 ℃, the roller spacing is less than 0.5mm, after 3-4 min of open milling, the roller spacing is adjusted to 2-3 mm, the roller temperature is maintained at 50 ℃, after 6-10 min of open milling, the roller spacing is adjusted to be less than 0.5mm, and triangular bags are formed for 6-8 times.
The invention also provides an ethylene-vinyl acetate rubber heat-resistant cable material which is prepared by the preparation method of the ethylene-vinyl acetate rubber heat-resistant cable material and comprises the following components in parts by mass: 26-45 parts of a rubber base material, 25-40 parts of a filling reinforcing agent, 2-7 parts of a crosslinking composition, 3.5-12.5 parts of a function maintaining composition, 0-1 part of a coloring agent and 0-1 part of a processing aid.
Preferably, the rubber base material comprises the following components in parts by mass: 25-40 parts of ethylene-vinyl acetate rubber and 1-5 parts of ethylene-propylene rubber.
Preferably, the crosslinking composition comprises the following components in parts by weight: 1-3 parts of a crosslinking agent and 1-4 parts of a crosslinking assistant.
Preferably, the function maintaining composition comprises the following components in parts by weight: 2.5-6 parts of plasticizer, 0.5-5 parts of stabilizer and 0.5-1.5 parts of anti-aging agent.
Preferably, the mass ratio of the plasticizer to the filling reinforcing agent is 1: 2-8, wherein the mass percent of the anti-aging agent to the crosslinking composition is 0.5-3%: 1.
specifically, the filling reinforcing agent is one or more of talcum powder, calcined kaolin, white carbon black or carbon black; for example, when preparing a light-colored cable material, the filler reinforcing agent is preferably calcined kaolin; when the black cable material is prepared, the filling reinforcing agent is preferably a mixture of calcined kaolin and carbon black, and the dosage of the calcined kaolin is 1-5 times of that of the carbon black; the type of the filling reinforcing agent can be freely selected according to different performance requirements and color system requirements, and the calcined kaolin can improve the voltage-resistant insulating property of the cable material, can also improve the high-temperature aging-resistant property and the high-temperature insulating property of the cable material, and has better reinforcing effect; the carbon black effectively improves the heat resistance and ageing resistance of the cable material.
Specifically, the viscosity of the plasticizer is 50-200 mPa & s; the plasticizer is one or more of dioctyl adipate (DOA), dioctyl sebacate (DOS), trioctyl trimellitate (TOTM), dioctyl terephthalate (DOTP) and epoxidized soybean oil, preferably, the plasticizer is a mixture of trioctyl trimellitate and dioctyl adipate, the use amount of the trioctyl trimellitate is 2-3 times that of the dioctyl adipate, plasticity of the cable material is further optimized, and heat resistance and low-temperature bending performance of the cable material are balanced.
Specifically, the particle size of the stabilizer is 100 nm-150 nm; the stabilizer is a mixture of two or more of magnesium oxide, zinc stearate, calcium stearate and zinc calcium stearate, and preferably the stabilizer is a mixture of magnesium oxide, zinc stearate, calcium stearate and zinc calcium stearate in a mass ratio of 1-2: the mixture of magnesium oxide and calcium zinc stearate of the cable material 1 effectively improves the stability of the cable material and improves the heat-resisting effect of the cable material.
Specifically, the anti-aging agent is one or more of 2, 2, 4-trimethyl-1, 2-dihydroquinoline polymer (RD), N' -di (beta-naphthyl) p-phenylenediamine (DNP), 2-Mercaptobenzimidazole (MB), and pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (1010), preferably, the anti-aging agent is a mixture of 2, 2, 4-trimethyl-1, 2-dihydroquinoline polymer (RD) and pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (1010), and the pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (1010) is used in an amount of 2, 2, the dosage of the 4-trimethyl-1, 2-dihydroquinoline polymer (RD) is 1-2 times that of the cable material, so that the heat resistance and the oxidation resistance of the cable material are effectively improved.
Preferably, the mass percentage of the cross-linking composition to the rubber substrate is 3-8%: 1, the mass ratio of the cross-linking agent to the cross-linking auxiliary agent is 1: 1 to 2.
Specifically, since the rubber substrate has little usability when it is not vulcanized and crosslinked by the crosslinking composition, the addition ratio of the crosslinking composition is strictly required. The crosslinking agent is peroxide, including but not limited to one or more of dicumyl peroxide (DCP), di-tert-butylperoxy diisopropylbenzene (BIBP), 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) -hexane (2.5B) and 1, 4-bis (tert-butylperoxyisopropyl) benzene (P), preferably, the crosslinking agent is di-tert-butylperoxy diisopropylbenzene (BIBP), and the crosslinking agent has small smell and better vulcanization flat period; the crosslinking assistant comprises but is not limited to triallyl cyanurate (TAC), triallyl isocyanurate (TAIC), Ethylene Dimethacrylate (EDMA), diallyl phthalate (DAP) and trimethylolpropane trimethacrylate (TMPTMA), and preferably, the crosslinking assistant adopts triallyl isocyanurate (TAIC), which does not affect scorching time and can obviously improve the vulcanization crosslinking effect; the preparation method of the invention adopts a two-step vulcanization process, and takes peroxide as the cross-linking agent, thereby effectively controlling the cross-linking degree and the uniformity of the cross-linking composition and the rubber substrate.
Preferably, the mass percentage of the ethylene propylene rubber to the rubber base material is 0-10%: 1; the Mooney viscosity of the ethylene-vinyl acetate rubber is 30-40 N.m, and the Mooney viscosity of the ethylene-propylene rubber is 20-35 N.m; the vinyl acetate content of the ethylene-vinyl acetate rubber is 65-80%, and the ethylene content of the ethylene-propylene rubber is 70-80%; preferably, the ethylene propylene rubber is a rubber composition consisting of 30-55 wt% of E-type ethylene propylene diene monomer with a third monomer of vinylidene norbornene, 10-25 wt% of D-type ethylene propylene diene monomer with a third monomer of dicyclopentadiene and 20-35 wt% of H-type ethylene propylene diene monomer with a third monomer of 1, 4-hexadiene, and the ethylene propylene rubber with a specific ratio is adopted to effectively promote the crosslinking polymerization degree and the tensile strength of the cable material to a proper range, so that the overall performance of the cable material is optimized; the ethylene-vinyl acetate rubber with the appropriate vinyl acetate content can improve the mixing and extrusion performance of the cable material, and can replace the traditional added flame retardant so as to meet the requirements of high flame retardance and heat resistance; secondly, the high ethylene content and the low Mooney viscosity of the ethylene propylene rubber effectively improve the vulcanization performance and the processing convenience of the cable material; the ethylene-vinyl acetate rubber is selected, the thermoplastic elastomer has high bond energy and has the advantages of high temperature resistance, aging resistance, good elasticity, good flexibility and the like, and the ethylene-propylene rubber with low viscosity is matched, because the main chain of the ethylene-vinyl acetate rubber is composed of chemically stable saturated hydrocarbon and only contains unsaturated double bonds in the side chain, the ethylene-propylene rubber has the properties of high temperature resistance, aging resistance and the like, under the action of the components such as the crosslinking composition and the like, the crosslinking performance between the ethylene-vinyl acetate rubber and the ethylene-propylene rubber is effectively promoted, the full vulcanization is ensured, and the synergistic effect of the ethylene-vinyl acetate rubber.
Specifically, the colorant is added with corresponding toner according to the color required by production, for example, when a blue cable material is prepared, the colorant is blue toner; when the red cable material is prepared, the colorant is red toner; the dosage of the composition accounts for 0.0005 to 0.01 percent of the total weight of the components; the processing aid is paraffin or PE wax, and the using amount of the processing aid accounts for 0-2% of the total weight of the components.
The preparation process according to the invention is now described in detail in the following examples:
example 1: the embodiment provides a preparation method of an ethylene-vinyl acetate rubber heat-resistant cable material, which comprises the following steps:
step 1, adding 25kg of calcined kaolin, 1.2kg of triallyl isocyanurate TAIC, 4kg of trioctyl trimellitate (TOTM), 0.5kg of tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester (1010), 0.5kg of 2, 2, 4-trimethyl-1, 2-dihydroquinoline polymer (RD), 0.08kg of blue toner, 3kg of magnesium oxide, 1.5kg of zinc calcium stearate, 3kg of ethylene propylene rubber (EPDM7001) and 32kg of ethylene-vinyl acetate rubber (EVM) into an internal rubber mixing mill in sequence, adding 200W microwave with power and 40kHz frequency ultrasonic waves, stopping the ultrasonic waves at intervals of 20s every 10s, carrying out banburying at 70 ℃ and 40r/min for 8min, heating to 80 ℃, carrying out banburying for 40min, keeping the rubber at 160 ℃, obtaining a mixture A; wherein the viscosity of trioctyl trimellitate (TOTM) is 150mPa & s, the particle size of magnesium oxide is 100nm, the Mooney viscosity of ethylene-vinyl acetate rubber is 35N & m, the Mooney viscosity of ethylene-propylene rubber is 25N & m, the vinyl acetate content of the ethylene-vinyl acetate rubber is 65%, the ethylene content of the ethylene-propylene rubber is 70%, the ethylene-propylene rubber adopts a rubber composition consisting of 30 wt% of E type ethylene-propylene-diene monomer with a third monomer of vinylidene norbornene, 15 wt% of D type ethylene-propylene-diene monomer with a third monomer of dicyclopentadiene and 25 wt% of H type ethylene-propylene-diene monomer with a third monomer of 1, 4-hexadiene;
step 2, adding 1.2kg of di-tert-butyl dicumyl peroxide (BIBP) into the mixture A in an open rubber mixing mill, assisting with 200W microwave, 200W ultrasonic wave with frequency of 40kHz, stopping the ultrasonic wave every 10s, setting the roll temperature to be 45 ℃ and the roll distance to be 0.4mm, adjusting the roll distance to be 2mm after 3min of open mixing, maintaining the roll temperature to be 50 ℃, adjusting the roll distance to be 0.4mm after 6min of open mixing, and performing triangular bag packing for 6 times to obtain a mixture B;
step 3, assisting with 200W microwave, 200W ultrasonic wave with frequency of 40kHz, intermittently stopping the ultrasonic wave for 20s every 10s, extruding, vulcanizing and crosslinking the mixture B by adopting a two-step extrusion and vulcanization condition to obtain the blue ethylene-vinyl acetate rubber heat-resistant cable material;
in the extrusion vulcanization condition, saturated steam is adopted in the first vulcanization step, and constant-temperature air-blast oil seal is adopted in the second vulcanization step;
the first vulcanization step conditions were: vulcanizing pressure is 2MPa, time is 3min, an extruder comprising a three-section type 100m vulcanizing pipeline is adopted, the temperature of a machine body and a machine head of the extruder is respectively 50 ℃ and 53 ℃, the temperature of a first section is 200 ℃, the temperature of a second section is 220 ℃, and the temperature of a third section is 230 ℃;
the second sulfurization step conditions are as follows: the temperature is 150 ℃, and the time is 1 h; the temperature is 220 ℃ and the time is 4 h.
The ethylene-vinyl acetate rubber heat-resistant cable material prepared in example 1 was subjected to performance parameter measurement. The performance parameters of the conventional cable material and the cable material of example 1 were measured before aging and after aging at 150 ℃ for 10 days. The results of the measurements of the specific performance parameters are shown in Table 1.
TABLE 1 determination of specific Cable Material Performance parameters
| Elongation at break% | Breaking force N | Tensile strength N/mm2 | Cross section area mm2 | |
| Traditional cable material | ≥200 | ≥6.5 | ||
| Before aging | 270 | 32.3 | 8.4 | 3.85 |
| Aging at 150 deg.C for 10 days | 280 | 35.0 | 9.1 | |
| Rate of change | 3.7％ | 8.3％ | ||
| Standard of change rate | ±30％ | ±30％ | ||
| The result of the judgment | Qualified |
Example 2: the embodiment provides a preparation method of an ethylene-vinyl acetate rubber heat-resistant cable material, which comprises the following steps:
step 1, adding 25kg of calcined kaolin, 1.2kg of triallyl isocyanurate TAIC, 4kg of trioctyl trimellitate (TOTM), 0.5kg of tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester (1010), 0.5kg of 2, 2, 4-trimethyl-1, 2-dihydroquinoline polymer (RD), 0.06kg of red toner, 0.01kg of carbon black N660, 3kg of magnesium oxide, 1.5kg of zinc calcium stearate, 3kg of ethylene propylene rubber (EPDM7001) and 32kg of ethylene-vinyl acetate rubber (EVM) into an internal rubber mixing mill in sequence, adding 200W microwave, 100W ultrasonic wave with frequency of 60kHz, stopping the ultrasonic wave for 20s every 10s, heating to 120 ℃ and mixing for 40min under the conditions of 90 ℃ and 40r/min, maintaining the glue temperature to 160 ℃ to obtain a mixture A; wherein the viscosity of trioctyl trimellitate (TOTM) is 150mPa & s, the particle size of magnesium oxide is 100nm, the Mooney viscosity of ethylene-vinyl acetate rubber is 35N & m, the Mooney viscosity of ethylene-propylene rubber is 25N & m, the vinyl acetate content of the ethylene-vinyl acetate rubber is 65%, the ethylene content of the ethylene-propylene rubber is 70%, the ethylene-propylene rubber adopts a rubber composition consisting of 30 wt% of E type ethylene-propylene-diene monomer with a third monomer of vinylidene norbornene, 15 wt% of D type ethylene-propylene-diene monomer with a third monomer of dicyclopentadiene and 25 wt% of H type ethylene-propylene-diene monomer with a third monomer of 1, 4-hexadiene;
step 2, adding 1.2kg of di-tert-butyl dicumyl peroxide (BIBP) into the mixture A in an open rubber mixing mill, assisting with microwaves with the power of 200W, ultrasonic waves with the power of 100W and the frequency of 60kHz, stopping the ultrasonic waves every 10s, setting the roll temperature to be 45 ℃ and the roll distance to be 0.45mm, adjusting the roll distance to be 3mm after open milling for 4min, maintaining the roll temperature to be 50 ℃, adjusting the roll distance to be 0.45mm after open milling for 8min, and performing triangular bag packing for 8 times to obtain a mixture B;
step 3, assisting by using ultrasonic waves with the power of 200W, the power of 100W and the frequency of 60kHz, stopping the ultrasonic waves intermittently for 20s every 10s, extruding, vulcanizing and crosslinking the mixture B by adopting a two-step extrusion and vulcanization condition to obtain a brown ethylene-vinyl acetate rubber heat-resistant cable material;
in the extrusion vulcanization condition, saturated steam is adopted in the first vulcanization step, and constant-temperature air-blast oil seal is adopted in the second vulcanization step;
the first vulcanization step conditions were: vulcanizing pressure is 1.85MPa, time is 6min, an extruder comprising a three-section type 100m vulcanizing pipeline is adopted, the temperature of a machine body and a machine head is respectively 50 ℃ and 53 ℃, the temperature of a first section is 200 ℃, the temperature of a second section is 210 ℃, and the temperature of a third section is 230 ℃;
the second sulfurization step conditions are as follows: the temperature is 140 ℃, and the time is 1 h; the temperature is 220 ℃ and the time is 4 h.
The ethylene-vinyl acetate rubber heat-resistant cable material prepared in example 2 was subjected to performance parameter measurement. The performance parameters of the conventional cable material and the cable material of example 2 were measured before aging and after aging at 150 ℃ for 10 days. The results of the measurements of the specific performance parameters are shown in Table 2.
TABLE 2 specific performance parameter measurement results of cable materials
| Elongation at break% | Breaking force N | Tensile strength N/mm2 | Cross section area mm2 | |
| Traditional cable material | ≥200 | ≥6.5 | ||
| Before aging | 260 | 35.0 | 9.1 | 3.85 |
| Aging at 150 deg.C for 10 days | 240 | 38.1 | 9.9 | |
| Rate of change | -7.7％ | 8.8％ | ||
| Standard of change rate | ±30％ | ±30％ | ||
| The result of the judgment | Qualified |
Example 3: the embodiment provides a preparation method of an ethylene-vinyl acetate rubber heat-resistant cable material, which comprises the following steps:
step 1, adding 18kg of calcined kaolin, 1.2kg of triallyl isocyanurate TAIC, 4kg of trioctyl trimellitate (TOTM), 0.8kg of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester (1010), 0.5kg of 2, 2, 4-trimethyl-1, 2-dihydroquinoline polymer (RD), 5kg of carbon black N660, 3kg of magnesium oxide, 1.5kg of zinc calcium stearate, 1kg of ethylene propylene rubber (EPDM7001) and 35kg of ethylene-vinyl acetate rubber (EVM) into an internal rubber mixing mill in sequence, adding 200W microwave with the power of 100W and the frequency of 60kHz, stopping the ultrasonic wave intermittently for 20s every 10s, carrying out banburying at the temperature of 90 ℃ and the rotating speed of 40r/min for 10min, heating to 120 ℃, carrying out banburying for 40min, keeping the temperature of the rubber to 160 ℃, obtaining a mixture A; wherein the viscosity of trioctyl trimellitate (TOTM) is 150mPa & s, the particle size of magnesium oxide is 100nm, the Mooney viscosity of ethylene-vinyl acetate rubber is 35N & m, the Mooney viscosity of ethylene-propylene rubber is 25N & m, the vinyl acetate content of the ethylene-vinyl acetate rubber is 65%, the ethylene content of the ethylene-propylene rubber is 70%, the ethylene-propylene rubber adopts a rubber composition consisting of 30 wt% of E type ethylene-propylene-diene monomer with a third monomer of vinylidene norbornene, 15 wt% of D type ethylene-propylene-diene monomer with a third monomer of dicyclopentadiene and 25 wt% of H type ethylene-propylene-diene monomer with a third monomer of 1, 4-hexadiene;
step 2, adding 1.2kg of di-tert-butyl dicumyl peroxide (BIBP) into the mixture A in an open rubber mixing mill, assisting with microwaves with the power of 200W, ultrasonic waves with the power of 100W and the frequency of 60kHz, stopping the ultrasonic waves every 10s, setting the roll temperature to be 45 ℃ and the roll distance to be 0.45mm, adjusting the roll distance to be 3mm after open milling for 4min, maintaining the roll temperature to be 50 ℃, adjusting the roll distance to be 0.45mm after open milling for 8min, and performing triangular bag packing for 8 times to obtain a mixture B;
step 3, assisting by using ultrasonic waves with the power of 200W, the power of 100W and the frequency of 60kHz, stopping the ultrasonic waves intermittently for 20s every 10s, extruding, vulcanizing and crosslinking the mixture B by adopting a two-step extrusion and vulcanization condition to obtain a brown ethylene-vinyl acetate rubber heat-resistant cable material;
in the extrusion vulcanization condition, saturated steam is adopted in the first vulcanization step, and constant-temperature air-blast oil seal is adopted in the second vulcanization step;
the first vulcanization step conditions were: vulcanizing pressure is 1.85MPa, time is 6min, an extruder comprising a three-section type 100m vulcanizing pipeline is adopted, the temperature of a machine body and a machine head is respectively 50 ℃ and 53 ℃, the temperature of a first section is 200 ℃, the temperature of a second section is 210 ℃, and the temperature of a third section is 230 ℃;
the second sulfurization step conditions are as follows: the temperature is 140 ℃, and the time is 1 h; the temperature is 220 ℃ and the time is 4 h.
The ethylene-vinyl acetate rubber heat-resistant cable material prepared in example 3 was subjected to performance parameter measurement. The performance parameters of the conventional cable material and the cable material of example 3 were measured before aging and after aging at 150 ℃ for 10 days. The results of the measurements of the specific performance parameters are shown in Table 3.
TABLE 3 determination of specific performance parameters of cable materials
| Elongation at break% | Breaking force N | Tensile strength N/mm2 | Cross section area mm2 | |
| Traditional cable material | ≥200 | ≥6.5 | ||
| Before aging | 380 | 36.8 | 11.5 | 3.2 |
| Aging at 150 deg.C for 10 days | 360 | 33.3 | 10.4 | |
| Rate of change | -5.3％ | 9.6％ | ||
| Standard of change rate | ±30％ | ±30％ | ||
| The result of the judgment | Qualified |
In summary, the present invention has the following advantages:
(1) according to the invention, through the optimization of the selection and content of each component, the improvement of the preparation process and the synergistic cooperation effect, the cable material with high temperature resistance, aging resistance, high strength and high toughness is manufactured and is used for coating the outer periphery of the wire, so that the power line meets the requirements of heat resistance at 110 ℃ and aging resistance;
(2) the mixing process conditions have great influence on the performance of the mixed cable material, and the method aims to improve the dispersion uniformity of each component in a rubber system, ensure the uniform dispersion of each component by controlling the feeding sequence, the closed mixing conditions, the open mixing conditions and the like, eliminate internal stress and ensure good mixing quality and high performance of products;
(3) various components are sequentially added to create a dispersion system with strong dispersion compatibility, and the crosslinking interaction between the ethylene propylene rubber and the ethylene-vinyl acetate rubber is enhanced under the action of a crosslinking agent and a crosslinking assistant by utilizing the chemical reaction between the ethylene propylene rubber and the ethylene-vinyl acetate rubber, so that the strong combination of the ethylene propylene rubber and the ethylene-vinyl acetate rubber is realized, and the comprehensive performance of the cable material is further optimized;
(4) proper ultrasonic waves and microwaves are supplemented in the preparation process, and due to the synergy of the ultrasonic waves and the microwaves, the rubber base material and the crosslinking composition are promoted to be fully copolymerized and crosslinked, so that the vulcanization effect and efficiency are further improved, and the comprehensive performance of the cable material is optimized;
(5) the two-step extrusion vulcanization condition is adopted, and peroxide is used as a crosslinking agent, so that the crosslinking degree and the uniformity of the crosslinking composition and the rubber base material are effectively controlled, the rubber system is promoted to be crosslinked mutually under different vulcanization environments, the vulcanization speed and the process adaptability of continuous production are improved, and the quality stability of products is improved;
(6) the ethylene propylene rubber with a specific ratio is adopted, so that the crosslinking polymerization degree and the tensile strength of the cable material are effectively promoted to a proper range, and the overall performance of the cable material is optimized; the ethylene-vinyl acetate rubber with the appropriate vinyl acetate content can improve the mixing and extrusion performance of the cable material, and can replace the traditional added flame retardant so as to meet the requirements of high flame retardance and heat resistance; secondly, the high ethylene content and the low Mooney viscosity of the ethylene propylene rubber effectively improve the vulcanization performance and the processing convenience of the cable material; the ethylene-vinyl acetate rubber is selected, the thermoplastic elastomer has high bond energy, and has the advantages of high temperature resistance, aging resistance, good elasticity, good flexibility and the like, and the ethylene-propylene rubber with low viscosity is matched, as the main chain of the ethylene-vinyl acetate rubber is composed of chemically stable saturated hydrocarbon, only unsaturated double bonds are contained in the side chain, the ethylene-propylene rubber has the properties of high temperature resistance, aging resistance and the like, under the action of the components such as the crosslinking composition and the like, the crosslinking performance between the ethylene-vinyl acetate rubber and the ethylene-propylene rubber is effectively promoted, the full vulcanization is ensured, and the synergistic effect of the ethylene-vinyl;
(7) the proper amount of the filling reinforcing agent can improve the voltage-resistant insulating property of the cable material, can also improve the high-temperature aging-resistant property and the high-temperature insulating property of the cable material, and has better reinforcing effect; the stabilizer is used for maintaining the crosslinking stability of the cable material in the vulcanization process and further optimizing the comprehensive performance of the cable material.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. Those skilled in the art can make many possible variations and modifications to the invention using the above disclosed technical means and teachings, or can modify equivalent embodiments with equivalent variations, without departing from the scope of the invention. Therefore, all equivalent changes made according to the shape, structure and principle of the present invention should be covered by the protection scope of the present invention without departing from the contents of the technical scheme of the present invention.
Claims (10)
1. The preparation method of the ethylene-vinyl acetate rubber heat-resistant cable material is characterized by comprising the following steps:
step 1, sequentially adding the components according to the formula amount, and uniformly dispersing under the conditions of ultrasonic waves and microwaves under the closed mixing condition to obtain a mixture A;
step 2, adding the cross-linking agent into the mixture A under the open mixing condition with the assistance of ultrasonic waves and microwaves, turning uniformly, and rolling to obtain a mixture B;
and 3, extruding, vulcanizing and crosslinking the mixture B under the extrusion vulcanization condition by assisting ultrasonic waves and microwaves to obtain the ethylene-vinyl acetate rubber heat-resistant cable material.
2. The method for preparing the ethylene-vinyl acetate rubber heat-resistant cable material according to claim 1, wherein the adding sequence of the components in the step 1 is as follows: sequentially adding a filling reinforcing agent, a crosslinking assistant, a plasticizer, an anti-aging agent, a coloring agent, a processing assistant, ethylene propylene rubber and ethylene-vinyl acetate rubber.
3. The method for preparing the ethylene-vinyl acetate rubber heat-resistant cable material according to claim 2, wherein in the step 3, the extrusion vulcanization conditions are two-step reaction, wherein saturated steam is used in the first vulcanization step, and constant temperature air-blast oil seal is used in the second vulcanization step;
the first vulcanization step conditions were: vulcanizing pressure is 1.7-2 MPa, time is 1-6 min, an extruder comprising a three-section type 100m vulcanizing pipeline is adopted, the temperature of a machine body and a machine head of the extruder is 50 ℃ and 53 ℃, the temperature of a first section is 200 ℃, the temperature of a second section is 210-220 ℃, and the temperature of a third section is 230 ℃;
the second sulfurization step conditions are as follows: the temperature is 130-150 ℃, and the time is 1-1.5 h; the temperature is 180-220 ℃, and the time is 2.5-4 h.
4. An ethylene-vinyl acetate rubber heat-resistant cable material, which is characterized by being prepared by the preparation method of the ethylene-vinyl acetate rubber heat-resistant cable material as claimed in any one of claims 1 to 3, wherein the cable material comprises the following components in parts by mass: 26-45 parts of a rubber base material, 25-40 parts of a filling reinforcing agent, 2-7 parts of a crosslinking composition, 3.5-12.5 parts of a function maintaining composition, 0-1 part of a coloring agent and 0-1 part of a processing aid.
5. The ethylene-vinyl acetate rubber heat-resistant cable material as claimed in claim 4, wherein the rubber base material comprises the following components in parts by mass: 25-40 parts of ethylene-vinyl acetate rubber and 1-5 parts of ethylene-propylene rubber.
6. The ethylene-vinyl acetate rubber heat-resistant cable material according to claim 5, wherein the crosslinking composition comprises the following components in parts by mass: 1-3 parts of a crosslinking agent and 1-4 parts of a crosslinking assistant.
7. The ethylene-vinyl acetate rubber heat-resistant cable material according to claim 6, wherein the function-maintaining composition comprises the following components in parts by mass: 2.5-6 parts of plasticizer, 0.5-5 parts of stabilizer and 0.5-1.5 parts of anti-aging agent.
8. The ethylene-vinyl acetate rubber heat-resistant cable material according to claim 7, wherein the mass ratio of the plasticizer to the filling reinforcing agent is 1: 2-8, wherein the mass percent of the anti-aging agent to the crosslinking composition is 0.5-3%: 1.
9. the ethylene-vinyl acetate rubber heat-resistant cable material according to claim 8, wherein the mass percentage of the cross-linking composition to the rubber base material is 3-8%: 1, the mass ratio of the cross-linking agent to the cross-linking auxiliary agent is 1: 1 to 2.
10. The ethylene-vinyl acetate rubber heat-resistant cable material as claimed in claim 9, wherein the mass percentage of the ethylene-propylene rubber to the rubber base material is 0-10%: 1.
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