CN114874556B - Flame-retardant ethylene propylene diene monomer rubber sleeve for cable and preparation method thereof - Google Patents
Flame-retardant ethylene propylene diene monomer rubber sleeve for cable and preparation method thereof Download PDFInfo
- Publication number
- CN114874556B CN114874556B CN202210397247.6A CN202210397247A CN114874556B CN 114874556 B CN114874556 B CN 114874556B CN 202210397247 A CN202210397247 A CN 202210397247A CN 114874556 B CN114874556 B CN 114874556B
- Authority
- CN
- China
- Prior art keywords
- parts
- ethylene propylene
- diene monomer
- propylene diene
- rubber sleeve
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A30/00—Adapting or protecting infrastructure or their operation
- Y02A30/14—Extreme weather resilient electric power supply systems, e.g. strengthening power lines or underground power cables
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The application discloses a flame-retardant ethylene propylene diene monomer rubber sleeve for cables and a preparation method thereof, wherein the rubber sleeve is obtained by crosslinking ethylene propylene diene monomer rubber and polymer modified clay aerogel, and the polymer modified clay aerogel comprises the following components: phosphate flame retardant, clay aerogel. According to the application, the phosphate flame retardant containing siloxane is loaded on the surface of clay to prepare aerogel through hydroxyl silicone oil and hexamethyldisilazane, so that polymer modified clay aerogel with a coating structure is formed, then the polymer modified clay aerogel is crosslinked with ethylene propylene diene monomer rubber and is mixed with carbon black and other materials, and the polymer modified clay aerogel is applied to rubber sleeve products, and when the polymer modified clay aerogel is combusted, a solid-phase flame-retardant structure with mutually penetrated and embedded silicon layers, carbon layers and carbon black is formed, so that the flame retardant performance of the ethylene propylene diene monomer rubber is enhanced.
Description
Technical Field
The application relates to the technical field of rubber sleeves, in particular to a flame-retardant ethylene propylene diene monomer rubber sleeve for cables and a preparation method thereof.
Background
The ethylene-propylene-small-amount non-conjugated diene copolymer is ethylene propylene diene monomer, the molecular main chain of the ethylene propylene diene monomer is completely saturated, the ethylene propylene diene monomer has the characteristics of excellent weather aging resistance, heat resistance, water resistance, chemical medium resistance and the like, the application field is wide, and the rubber sleeve for the cable is one application of the ethylene propylene diene monomer. But the ethylene propylene diene monomer rubber has poorer flame retardant property, is influenced by circuit short circuit and external environment in a cable, is easy to burn, and is decomposed into combustible low-molecular substances at high temperature, so that the burning reaction is aggravated, and more serious loss is caused. Therefore, we propose a flame-retardant ethylene propylene diene monomer rubber sleeve for cables and a preparation method thereof.
Disclosure of Invention
The application aims to provide a flame-retardant ethylene propylene diene monomer rubber sleeve for a cable and a preparation method thereof, so as to solve the problems in the background technology.
In order to solve the technical problems, the application provides the following technical scheme: the flame-retardant ethylene propylene diene monomer rubber sleeve for the cable is obtained by crosslinking ethylene propylene diene monomer rubber and polymer modified clay aerogel, and the polymer modified clay aerogel comprises components of phosphate flame retardant and clay aerogel.
Further, the paint comprises the following components in parts by weight: 100 parts of ethylene propylene diene monomer, 10-24 parts of phosphate flame retardant, 10-25 parts of clay aerogel, 130-160 parts of carbon black, 8-18 parts of cross-linking agent, 1.5-4.5 parts of auxiliary cross-linking agent, 8-14 parts of auxiliary agent, 1-6 parts of hydroxyl silicone oil and 3-7 parts of hexamethyldisilazane.
Further, the cross-linking agent is dicumyl peroxide, and the auxiliary agent is one or more of 3-5 parts of zinc oxide, 2-3 parts of anti-aging agent and 3-6 parts of paraffin oil.
The preparation method of the flame-retardant ethylene propylene diene monomer rubber sleeve for the cable comprises the following steps:
(1) Preparation of phosphate flame retardant:
taking phosphorus oxychloride to react with melamine; then sequentially reacting with amino rosin derivatives and epoxy siloxane to obtain a phosphate flame retardant;
(2) Preparation of polymer modified clay aerogel:
mixing a phosphate flame retardant, clay aerogel, hydroxyl silicone oil and hexamethyldisilazane to obtain polymer modified clay aerogel;
(3) Preparation of a rubber sleeve:
mixing ethylene propylene diene monomer rubber, carbon black and an auxiliary agent; adding polymer modified clay aerogel, a cross-linking agent and an auxiliary cross-linking agent, cross-linking and extruding to obtain the rubber sleeve.
Further, the (1) comprises the following processes:
1.1. adding pentaerythritol, phosphorus trichloride and triethylamine into o-dichlorobenzene, heating to 80-100 ℃ under the protection of nitrogen atmosphere, and reacting for 5-20 h to obtain a product A;
1.2. taking melamine, a product A and triethylamine, heating to 60-75 ℃, and reacting for 10-40 min to obtain a product B;
1.3. taking dimethylbenzene, adding polymerized rosin, 4-dimethylaminopyridine and triethylamine, heating to 40-60 ℃, slowly adding a mixed solution of diethylenetriamine and dimethylbenzene, and reacting for 8-12 hours to obtain an amino-containing rosin derivative;
1.4. mixing the product B with the amino-containing rosin derivative, heating to 70-85 ℃, and reacting for 30-60 min; adding gamma-glycidoxypropyl trimethoxy silane, and reacting for 60-90 min at a constant temperature of 80-90 ℃ under the protection of nitrogen to obtain the phosphate flame retardant.
Further, the mole ratio of pentaerythritol and phosphorus trichloride in the 1.1 is 1 (1.0-1.1).
Further, the mole ratio of melamine and phosphoryl chloride in the 1.2 is 1.0 (3.0-3.6).
Further, the molar ratio of polymerized rosin to diethylenetriamine in the 1.3 is 1 (1.0-1.2).
Further, the molar ratio of the product B, the amino-containing rosin derivative and the gamma-glycidoxypropyl trimethoxysilane in the 1.4 is 1 (0.5-0.7) to 0.3-0.5.
In the technical scheme, pentaerythritol reacts with phosphorus trichloride to obtain pentaerythritol phosphoryl chloride, wherein the phosphoryl chloride group reacts with amino in melamine to obtain a product B with high heat stability and high-temperature residues; achieving good flame-retardant effect; reacting polymerized rosin with diethylenetriamine to obtain amino-containing rosin derivatives; the phosphoryl chloride in the product B reacts with amino rosin derivative and gamma-glycidoxypropyl trimethoxy silane to finally obtain a phosphate flame retardant;
the prepared phosphate flame retardant can be cooperated with carbon black, in the combustion process, phosphoric acid micromolecules generated by decomposition of the phosphate flame retardant have stronger water absorption, so that the surface of a burnt polymer is carbonized and filled into pores of the carbon black to form an interpenetrating embedded carbon layer, and nitrogen, carbon and silicon in the phosphate flame retardant can help the polymer to form carbon, inhibit the melting behavior of the polymer and better play the solid flame retardant effect of the carbon layer; the release of volatile components in the carbon layer can be reduced, heat and oxygen are isolated, the oxidation heat of burning polymers is reduced, and the effects of inhibiting burning and solid-phase flame retardance are achieved; meanwhile, phosphoric acid micromolecules overflow, free radicals in the combustion atmosphere can be captured, the oxidation reaction chain of combustion is cut off, ammonia gas, nitrogen gas and the like generated by the combustion of a nitrogen source in the phosphate flame retardant are cooperated, and combustible gas in the rubber sleeve environment is diluted, so that the gas-phase flame retardant effect is achieved;
further, the (2) comprises the following processes:
mixing clay with deionized water, and stirring at high speed for 5-10 min; adding p-toluenesulfonic acid, regulating the pH of the system to 6, stirring for 10-15 min, pouring into a mould, freezing with liquid nitrogen, drying at room temperature under vacuum for 4-6 d and the vacuum degree of 8-12 Pa to obtain aerogel;
mixing a phosphate flame retardant, clay aerogel, hydroxyl silicone oil and hexamethyldisilazane, stirring for 15-20 min under the protection of dry nitrogen, and adding a catalyst dibutyl tin dilaurate; defoaming, putting into a mould, and curing for 7-8 d at room temperature to obtain the polymer modified clay aerogel.
In the technical scheme, clay (sodium montmorillonite) is used for preparing aerogel, and the aerogel is mixed with phosphate flame retardant, hydroxy silicone oil and hexamethyldisilazane, so that the mixture is subjected to a crosslinking reaction in a system in which the aerogel exists, the phosphate flame retardant is fixed in pores of the aerogel by using the hydroxy silicone oil and the hexamethyldisilazane to form a jogged structure, the strength and the continuity of a carbon layer are improved, the solid-phase flame retardant effect is enhanced, and the introduction of a clay aerogel substrate can reduce the heat conducting property of the carbon layer and prevent heat transmission during combustion, so that the flame retardant property of the prepared rubber sleeve is improved; meanwhile, swelling of the phosphate flame retardant in an ethylene propylene diene monomer system can be avoided, corrosion to the ethylene propylene diene monomer is prevented, and the resistance of the manufactured rubber sleeve is prevented from being influenced;
further, the mixing process in (3) is as follows: heating to 60-80 deg.c and plasticating for 10-20 min.
Further, the crosslinking process in (3) is as follows: primary crosslinking: the temperature is 120-170 ℃, the time is 15-20 min, and the pressure is 10-12 Mpa; secondary crosslinking: the temperature is 210-220 ℃ and the time is 3-5 h.
In the technical scheme, ethylene propylene diene monomer and polymer modified clay aerogel are crosslinked under the action of a crosslinking agent and auxiliary crosslinking agent trimethylolpropane trimethacrylate, so that flame retardant property is realized; meanwhile, due to the high-rigidity structure such as phenanthrene ring in the double bond-containing phosphate flame retardant, the mechanical property of the prepared rubber sleeve can be improved, the crosslinking density of the rubber sleeve is increased, the compatibility between ethylene propylene diene monomer rubber and polymer modified clay aerogel can be improved, microphase separation is reduced, and the mechanical property of the prepared rubber sleeve is further improved;
compared with the prior art, the application has the following beneficial effects:
according to the flame-retardant ethylene propylene diene monomer rubber sleeve for the cable and the preparation method thereof, the phosphate flame retardant containing siloxane is loaded on clay to prepare aerogel surface through hydroxy silicone oil and hexamethyldisilazane, so that polymer modified clay aerogel with a coating structure is formed, then the polymer modified clay aerogel is crosslinked with ethylene propylene diene monomer rubber and is mixed with materials such as carbon black, and the ethylene propylene diene monomer rubber sleeve is applied to rubber sleeve products, and a solid-phase flame-retardant structure with mutually penetrated and embedded silicon layers, carbon layers and carbon black is formed during combustion, so that the flame-retardant performance of the ethylene propylene diene monomer rubber is enhanced.
Detailed Description
The following description of the technical solutions in the embodiments of the present application will be clearly and completely described, and it is obvious that the described embodiments are only some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
Example 1
(1) Preparation of phosphate flame retardant:
1.1. adding pentaerythritol, phosphorus trichloride and triethylamine into o-dichlorobenzene, heating to 80 ℃ under the protection of nitrogen atmosphere, and reacting for 5 hours to obtain a product A; the molar ratio of pentaerythritol to phosphorus trichloride to triethylamine is 1:1:2.01;
1.2. taking melamine, a product A and triethylamine, heating to 60 ℃, and reacting for 10min to obtain a product B; the mole ratio of melamine to phosphorus oxychloride to triethylamine is 1.0:3.0:3.01;
1.3. taking dimethylbenzene, adding polymerized rosin, 4-dimethylaminopyridine and triethylamine, heating to 40 ℃, slowly adding a mixed solution of diethylenetriamine and dimethylbenzene, and reacting for 8 hours to obtain an amino-containing rosin derivative; the molar ratio of polymerized rosin to diethylenetriamine to triethylamine is 1:1:2.01; the dosage of the 4-dimethylaminopyridine is 3% of the reaction mass;
1.4. mixing the product B and the rosin derivative containing amino groups, heating to 70 ℃, and reacting for 30min; adding gamma-glycidoxypropyl trimethoxy silane, and reacting at a constant temperature of 80 ℃ for 60min under the protection of nitrogen to obtain a phosphate flame retardant; the molar ratio of the product B to the amino-containing rosin derivative to the gamma-glycidoxypropyl trimethoxysilane is 1:0.5:0.5;
(2) Preparation of polymer modified clay aerogel:
mixing clay with deionized water, and stirring at high speed for 5min; adding p-toluenesulfonic acid, regulating the pH of the system to 6, stirring for 10min, pouring into a mould, freezing with liquid nitrogen, drying at room temperature for 4d under vacuum, and obtaining aerogel with the vacuum degree of 8 Pa;
mixing phosphate flame retardant, clay aerogel, hydroxyl silicone oil and hexamethyldisilazane, stirring for 15min under the protection of dry nitrogen, and adding catalyst dibutyl tin dilaurate; defoaming, putting into a mold, and curing for 7d at room temperature to obtain polymer modified clay aerogel;
wherein, each component weight is as follows: 100 parts of ethylene propylene diene monomer, 10 parts of phosphate flame retardant, 10 parts of clay aerogel, 130 parts of carbon black, 8 parts of crosslinking agent dicumyl peroxide, 1.5 parts of auxiliary crosslinking agent trimethylolpropane trimethacrylate, 8 parts of auxiliary agent, 1 part of hydroxyl silicone oil and 3 parts of hexamethyldisilazane; the auxiliary agent comprises 3 parts of zinc oxide, 2 parts of an anti-aging agent and 3 parts of paraffin oil;
(3) Preparation of a rubber sleeve:
mixing ethylene propylene diene monomer, carbon black and an auxiliary agent, wherein the mixing process comprises the following steps: heating to 60 ℃, and plasticating for 10min; adding polymer modified clay aerogel, a crosslinking agent and an auxiliary crosslinking agent, and crosslinking, wherein the crosslinking process comprises the following steps: primary crosslinking: the temperature is 120 ℃, the time is 15min, and the pressure is 10Mpa; secondary crosslinking: the temperature is 210 ℃ and the time is 3 hours; extruding to obtain the rubber sleeve.
Example 2
(1) Preparation of phosphate flame retardant:
1.1. adding pentaerythritol, phosphorus trichloride and triethylamine into o-dichlorobenzene, heating to 90 ℃ under the protection of nitrogen atmosphere, and reacting for 12 hours to obtain a product A; the molar ratio of pentaerythritol to phosphorus trichloride to triethylamine is 1:1.05:2.02;
1.2. taking melamine, a product A and triethylamine, heating to 68 ℃, and reacting for 25min to obtain a product B; the mole ratio of melamine to phosphorus oxychloride to triethylamine is 1.0:3.3:3.02;
1.3. taking dimethylbenzene, adding polymerized rosin, 4-dimethylaminopyridine and triethylamine, heating to 50 ℃, slowly adding a mixed solution of diethylenetriamine and dimethylbenzene, and reacting for 10 hours to obtain an amino-containing rosin derivative; the molar ratio of the polymerized rosin to the diethylenetriamine to the triethylamine is 1:1.1:2.01; the dosage of the 4-dimethylaminopyridine is 3% of the reaction mass;
1.4. mixing the product B with the amino-containing rosin derivative, heating to 78 ℃, and reacting for 45min; adding gamma-glycidoxypropyl trimethoxy silane, and reacting for 75min at a constant temperature of 85 ℃ under the protection of nitrogen to obtain a phosphate flame retardant; the molar ratio of the product B to the amino-containing rosin derivative to the gamma-glycidoxypropyl trimethoxysilane is 1:0.6:0.4;
(2) Preparation of polymer modified clay aerogel:
mixing clay with deionized water, and stirring at high speed for 8min; adding p-toluenesulfonic acid, regulating the pH of the system to 6, stirring for 12min, pouring into a mould, freezing with liquid nitrogen, drying at room temperature under vacuum for 5d, and obtaining aerogel with the vacuum degree of 10 Pa;
mixing phosphate flame retardant, clay aerogel, hydroxyl silicone oil and hexamethyldisilazane, stirring for 18min under the protection of dry nitrogen, and adding catalyst dibutyl tin dilaurate; defoaming, putting into a mold, and curing at room temperature for 7.5d to obtain polymer modified clay aerogel;
wherein, each component weight is as follows: 100 parts of ethylene propylene diene monomer, 17 parts of phosphate flame retardant, 17 parts of clay aerogel, 145 parts of carbon black, 13 parts of crosslinking agent dicumyl peroxide, 3 parts of auxiliary crosslinking agent trimethylolpropane trimethacrylate, 11 parts of auxiliary agent, 4 parts of hydroxyl silicone oil and 5 parts of hexamethyldisilazane; the auxiliary agent comprises 4 parts of zinc oxide, 3 parts of an anti-aging agent and 4 parts of paraffin oil;
(3) Preparation of a rubber sleeve:
mixing ethylene propylene diene monomer, carbon black and an auxiliary agent, wherein the mixing process comprises the following steps: heating to 70deg.C, and plasticating for 15min; adding polymer modified clay aerogel, a crosslinking agent and an auxiliary crosslinking agent, and crosslinking, wherein the crosslinking process comprises the following steps: primary crosslinking: the temperature is 145 ℃, the time is 18min, and the pressure is 11Mpa; secondary crosslinking: the temperature is 215 ℃ and the time is 4 hours; extruding to obtain the rubber sleeve.
Example 3
(1) Preparation of phosphate flame retardant:
1.1. adding pentaerythritol, phosphorus trichloride and triethylamine into o-dichlorobenzene, heating to 100 ℃ under the protection of nitrogen atmosphere, and reacting for 20 hours to obtain a product A; the molar ratio of pentaerythritol to phosphorus trichloride to triethylamine is 1:1.1:2.02;
1.2. taking melamine, a product A and triethylamine, heating to 75 ℃, and reacting for 40min to obtain a product B; the mole ratio of melamine to phosphorus oxychloride to triethylamine is 1.0:3.6:3.02;
1.3. taking dimethylbenzene, adding polymerized rosin, 4-dimethylaminopyridine and triethylamine, heating to 60 ℃, slowly adding a mixed solution of diethylenetriamine and dimethylbenzene, and reacting for 12 hours to obtain an amino-containing rosin derivative; the molar ratio of polymerized rosin, diethylenetriamine and triethylamine is 1:1.2:2.02; the dosage of the 4-dimethylaminopyridine is 3% of the reaction mass;
1.4. mixing the product B with the amino-containing rosin derivative, heating to 85 ℃, and reacting for 60min; adding gamma-glycidoxypropyl trimethoxy silane, and reacting for 90min at a constant temperature of 90 ℃ under the protection of nitrogen to obtain a phosphate flame retardant; the molar ratio of the product B to the amino-containing rosin derivative to the gamma-glycidoxypropyl trimethoxysilane is 1:0.7:0.5;
(2) Preparation of polymer modified clay aerogel:
mixing clay with deionized water, and stirring at high speed for 10min; adding p-toluenesulfonic acid, regulating the pH of the system to 6, stirring for 15min, pouring into a mould, freezing with liquid nitrogen, drying at room temperature under vacuum for 6d, and obtaining aerogel with the vacuum degree of 12 Pa;
mixing phosphate flame retardant, clay aerogel, hydroxyl silicone oil and hexamethyldisilazane, stirring for 20min under the protection of dry nitrogen, and adding catalyst dibutyl tin dilaurate; defoaming, putting into a mold, and curing for 8d at room temperature to obtain polymer modified clay aerogel;
wherein, each component weight is as follows: 100 parts of ethylene propylene diene monomer, 24 parts of phosphate flame retardant, 25 parts of clay aerogel, 160 parts of carbon black, 18 parts of crosslinking agent dicumyl peroxide, 4.5 parts of auxiliary crosslinking agent trimethylolpropane trimethacrylate, 14 parts of auxiliary agent, 6 parts of hydroxyl silicone oil and 7 parts of hexamethyldisilazane; the auxiliary agent comprises 5 parts of zinc oxide, 3 parts of an anti-aging agent and 6 parts of paraffin oil;
(3) Preparation of a rubber sleeve:
mixing ethylene propylene diene monomer, carbon black and an auxiliary agent, wherein the mixing process comprises the following steps: heating to 80 ℃, and plasticating for 20min; adding polymer modified clay aerogel, a crosslinking agent and an auxiliary crosslinking agent, and crosslinking, wherein the crosslinking process comprises the following steps: primary crosslinking: the temperature is 170 ℃, the time is 20min, and the pressure is 12Mpa; secondary crosslinking: the temperature is 220 ℃ and the time is 5 hours; extruding to obtain the rubber sleeve.
Comparative example 1
(1) Preparation of phosphate flame retardant:
1.1. adding pentaerythritol, phosphorus trichloride and triethylamine into o-dichlorobenzene, heating to 80 ℃ under the protection of nitrogen atmosphere, and reacting for 5 hours to obtain a product A; the molar ratio of pentaerythritol to phosphorus trichloride is 1:1;
1.2. taking melamine, a product A and triethylamine, heating to 60 ℃, and reacting for 10min to obtain a product B; the mole ratio of melamine to phosphoryl chloride is 1.0:3.0;
1.3. mixing the product B and diethylenetriamine, heating to 70 ℃, and reacting for 30min; adding gamma-glycidoxypropyl trimethoxy silane, and reacting at a constant temperature of 80 ℃ for 60min under the protection of nitrogen to obtain a phosphate flame retardant; the mol ratio of the product B to the diethylenetriamine to the gamma-glycidoxypropyl trimethoxysilane is 1:0.5:0.5;
steps (2) and (3) were the same as in example 1 to obtain rubber sleeves.
Comparative example 2
(1) Preparation of phosphate flame retardant:
1.1. adding pentaerythritol, phosphorus trichloride and triethylamine into o-dichlorobenzene, heating to 80 ℃ under the protection of nitrogen atmosphere, and reacting for 5 hours to obtain a product A; the molar ratio of pentaerythritol to phosphorus trichloride is 1:1;
1.2. taking melamine, a product A and triethylamine, heating to 60 ℃, and reacting for 10min to obtain a product B; the mole ratio of melamine to phosphoryl chloride is 1.0:3.0;
1.3. mixing the product B and diethylenetriamine, heating to 70 ℃, and reacting for 30min; obtaining a phosphate flame retardant; the mol ratio of the product B to the diethylenetriamine is 1:0.5;
(2) Preparation of polymer modified clay aerogel:
mixing clay with deionized water, and stirring at high speed for 5min; adding p-toluenesulfonic acid, regulating the pH of the system to 6, stirring for 10min, pouring into a mould, freezing with liquid nitrogen, drying at room temperature for 4d under vacuum, and obtaining aerogel with the vacuum degree of 8 Pa;
mixing phosphate flame retardant, clay aerogel, hydroxyl silicone oil, hexamethyldisilazane and gamma-glycidoxypropyl trimethoxysilane, stirring for 15min under the protection of dry nitrogen, and adding a catalyst dibutyl tin dilaurate; defoaming, putting into a mold, and curing for 7d at room temperature to obtain polymer modified clay aerogel;
wherein, each component weight is as follows: 100 parts of ethylene propylene diene monomer, 10 parts of phosphate flame retardant, 10 parts of clay aerogel, 130 parts of carbon black, 8 parts of crosslinking agent dicumyl peroxide, 1.5 parts of auxiliary crosslinking agent trimethylolpropane trimethacrylate, 8 parts of auxiliary agent, 1 part of hydroxyl silicone oil, 3 parts of hexamethyldisilazane and 3 parts of gamma-glycidoxypropyl trimethoxysilane; the auxiliary agent comprises 3 parts of zinc oxide, 2 parts of an anti-aging agent and 3 parts of paraffin oil;
step (3) was the same as in example 1 to obtain a rubber sleeve.
Comparative example 3
(2) Preparation of polymer modified clay aerogel:
mixing clay with deionized water, and stirring at high speed for 5min; adding p-toluenesulfonic acid, regulating the pH of the system to 6, stirring for 10min, pouring into a mould, freezing with liquid nitrogen, drying at room temperature for 4d under vacuum, and obtaining aerogel with the vacuum degree of 8 Pa;
mixing a phosphate flame retardant and clay aerogel, stirring for 15min under the protection of dry nitrogen, and adding a catalyst dibutyl tin dilaurate; defoaming, putting into a mold, and curing for 7d at room temperature to obtain polymer modified clay aerogel;
wherein, each component weight is as follows: 100 parts of ethylene propylene diene monomer, 10 parts of phosphate flame retardant, 10 parts of clay aerogel, 130 parts of carbon black, 8 parts of crosslinking agent dicumyl peroxide, 1.5 parts of auxiliary crosslinking agent trimethylolpropane trimethacrylate and 8 parts of auxiliary agent; the auxiliary agent comprises 3 parts of zinc oxide, 2 parts of an anti-aging agent and 3 parts of paraffin oil;
the steps (1) and (3) were the same as in comparative example 1, and rubber bushings were obtained.
Comparative example 4
(1) Preparation of phosphate flame retardant:
1.1. adding pentaerythritol, phosphorus trichloride and triethylamine into o-dichlorobenzene, heating to 80 ℃ under the protection of nitrogen atmosphere, and reacting for 5 hours to obtain a product A; the molar ratio of pentaerythritol to phosphorus trichloride is 1:1;
1.2. taking melamine, a product A and triethylamine, heating to 60 ℃, and reacting for 10min to obtain a product B; the mole ratio of melamine to phosphoryl chloride is 1.0:3.0;
1.3. taking dimethylbenzene, adding polymerized rosin, 4-dimethylaminopyridine and triethylamine, heating to 40 ℃, slowly adding a mixed solution of diethylenetriamine and dimethylbenzene, and reacting for 8 hours to obtain an amino-containing rosin derivative; the molar ratio of polymerized rosin to diethylenetriamine is 1:1;
1.4. mixing the product B and the rosin derivative containing amino groups, heating to 70 ℃, and reacting for 30min; adding gamma-glycidoxypropyl trimethoxy silane, and reacting at a constant temperature of 80 ℃ for 60min under the protection of nitrogen to obtain a phosphate flame retardant; the molar ratio of the product B to the amino-containing rosin derivative to the gamma-glycidoxypropyl trimethoxysilane is 1:0.5:0.5;
(2) Wherein, each component weight is as follows: 100 parts of ethylene propylene diene monomer, 10 parts of phosphate flame retardant, 130 parts of carbon black, 8 parts of crosslinking agent dicumyl peroxide, 1.5 parts of auxiliary crosslinking agent trimethylolpropane trimethacrylate, 8 parts of auxiliary agent, 1 part of hydroxyl silicone oil and 3 parts of hexamethyldisilazane; the auxiliary agent comprises 3 parts of zinc oxide, 2 parts of an anti-aging agent and 3 parts of paraffin oil;
step (3) was the same as in example 1 to obtain a rubber sleeve.
Comparative example 5
(1) Preparation of phosphate flame retardant:
1.1. adding pentaerythritol, phosphorus trichloride and triethylamine into o-dichlorobenzene, heating to 80 ℃ under the protection of nitrogen atmosphere, and reacting for 5 hours to obtain a product A; the molar ratio of pentaerythritol to phosphorus trichloride is 1:1;
1.2. taking melamine, a product A and triethylamine, heating to 60 ℃, and reacting for 10min to obtain a phosphate flame retardant; the mole ratio of melamine to phosphoryl chloride is 1.0:3.0;
(2) Wherein, each component weight is as follows: 100 parts of ethylene propylene diene monomer rubber, 10 parts of phosphate flame retardant, 130 parts of carbon black and 8 parts of auxiliary agent; the auxiliary agent comprises 3 parts of zinc oxide, 2 parts of an anti-aging agent and 3 parts of paraffin oil;
(2) Preparation of a rubber sleeve:
mixing ethylene propylene diene monomer, carbon black and an auxiliary agent, wherein the mixing process comprises the following steps: heating to 60 ℃, and plasticating for 10min; adding a phosphate flame retardant, a crosslinking agent and a crosslinking aid, and crosslinking, wherein the crosslinking process comprises the following steps: primary crosslinking: the temperature is 120 ℃, the time is 15min, and the pressure is 10Mpa; secondary crosslinking: the temperature is 210 ℃ and the time is 3 hours; extruding to obtain the rubber sleeve.
Experiment
Taking the rubber sleeves obtained in examples 1-3 and comparative examples 1-5, preparing test samples, respectively detecting the performances thereof and recording the detection results:
oxygen index: using GB/T10707-2008 as a test standard, and adopting a JF-3 type oxygen index tester to test a sample;
vertical combustion: using GB/T10707-2008 as a test standard, and adopting a CZF-3 type horizontal and vertical combustion tester to test a sample;
mechanical properties: using GB/T528-2009 as a test standard, and adopting a UTM4204X type electronic universal tester to test a sample;
from the data in the above table, the following conclusions can be clearly drawn:
the rubber sleeves obtained in examples 1 to 3 were compared with the rubber sleeves obtained in comparative examples 1 to 5, and it was found that the detection results,
1. compared with comparative example 5, the rubber sleeve obtained in examples 1-3 has more excellent oxygen index, vertical combustion, tensile strength and elongation at break data, which fully demonstrates that the preparation method of the application realizes the improvement of the flame retardant property and mechanical property of the ethylene propylene diene monomer rubber sleeve;
2. in comparison to example 1, the phosphate flame retardant of comparative example 1 does not add a component polymeric rosin; the oxygen index and the vertical burning data of the alloy are not obviously changed, and the tensile strength and the elongation at break data are obviously reduced, because: the rigid groups in the system are reduced by not adding the component polymerized rosin, so that the mechanical properties of the rubber sleeve are affected.
The phosphate flame retardant in comparative example 2 did not add component polymerized rosin and gamma-glycidoxypropyl trimethoxysilane was not incorporated into the phosphate flame retardant structure; the oxygen index data is slightly reduced, and the tensile strength and elongation at break data are further reduced, because: the gamma-glycidoxypropyl trimethoxysilane is not introduced into the structure of the phosphate flame retardant, so that the coating structure of the prepared polymer modified clay aerogel has defects, the compatibility between the phosphate flame retardant and ethylene propylene diene monomer rubber is poor, microphase separation occurs, and the mechanical property of the rubber sleeve is reduced;
the non-added components of comparative example 3, polymerized rosin, hydroxy silicone oil, hexamethyldisilazane, were all deteriorated in oxygen index, vertical burn, tensile strength, elongation at break data, because: the components of polymerized rosin, hydroxy silicone oil and hexamethyldisilazane are not added, so that the polymer modified clay aerogel has a carbon layer structure which is generated during combustion and the flame retardant property is reduced; the cross-linking between the polymer modified clay aerogel and the ethylene propylene diene monomer rubber is reduced, the compatibility is reduced, the microphase separation phenomenon is aggravated, and the mechanical properties of the prepared rubber sleeve are reduced;
the clay aerogel was not added in comparative example 4; the oxygen index, vertical burn, tensile strength, elongation at break data are all further degraded due to: the lack of clay aerogel can not establish a carbon layer structure as in the embodiment during combustion, so that the flame retardant property of the rubber layer is reduced; the free volume of the rubber is increased, the intermolecular acting force is weakened, and the mechanical property is reduced;
in conclusion, the flame retardant property and the mechanical property of the ethylene propylene diene monomer rubber sleeve are improved by setting the components and the preparation process.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process method article or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process method article or apparatus.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present application, and the present application is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present application has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (4)
1. A preparation method of a flame-retardant ethylene propylene diene monomer rubber sleeve for a cable is characterized by comprising the following steps: the preparation method comprises the following steps:
(1) Preparation of phosphate flame retardant:
1.1. adding pentaerythritol, phosphorus trichloride and triethylamine into o-dichlorobenzene, heating to 80-100 ℃ under the protection of nitrogen atmosphere, and reacting for 5-20 h to obtain a product A;
1.2. taking melamine, a product A and triethylamine, heating to 60-75 ℃, and reacting for 10-40 min to obtain a product B;
1.3. taking dimethylbenzene, adding polymerized rosin, 4-dimethylaminopyridine and triethylamine, heating to 40-60 ℃, slowly adding a mixed solution of diethylenetriamine and dimethylbenzene, and reacting for 8-12 hours to obtain an amino-containing rosin derivative;
1.4. mixing the product B with the amino-containing rosin derivative, heating to 70-85 ℃, and reacting for 30-60 min; adding gamma-glycidoxypropyl trimethoxy silane, and reacting for 60-90 min at a constant temperature of 80-90 ℃ under the protection of nitrogen to obtain a phosphate flame retardant;
(2) Preparation of polymer modified clay aerogel:
mixing clay with deionized water, and stirring at high speed for 5-10 min; adding p-toluenesulfonic acid, stirring for 10-15 min, pouring into a mould, freezing with liquid nitrogen, and drying at room temperature under vacuum for 4-6 d with the vacuum degree of 8-12 Pa to obtain aerogel;
mixing a phosphate flame retardant, clay aerogel, hydroxyl silicone oil and hexamethyldisilazane, stirring for 15-20 min under the protection of dry nitrogen, and adding a catalyst dibutyl tin dilaurate; defoaming, putting into a mould, and curing at room temperature for 7-8 d to obtain polymer modified clay aerogel;
(3) Preparation of a rubber sleeve:
mixing ethylene propylene diene monomer rubber, carbon black and an auxiliary agent; adding polymer modified clay aerogel, a cross-linking agent and an auxiliary cross-linking agent, cross-linking and extruding to obtain a rubber sleeve;
the mole ratio of pentaerythritol and phosphorus trichloride in the formula 1.1 is 1 (1.0-1.1); 1.2. the mole ratio of the melamine to the phosphoryl chloride is 1.0 (3.0-3.6);
the molar ratio of the polymerized rosin to the diethylenetriamine in the step 1.3 is 1 (1.0-1.2); 1.4. the molar ratio of the intermediate product B to the amino-containing rosin derivative to the gamma-glycidoxypropyl trimethoxysilane is 1 (0.5-0.7) (0.3-0.5);
the rubber sleeve comprises the following components in parts by weight: 100 parts of ethylene propylene diene monomer, 10-24 parts of phosphate flame retardant, 10-25 parts of clay aerogel, 130-160 parts of carbon black, 8-18 parts of cross-linking agent, 1.5-4.5 parts of auxiliary cross-linking agent, 8-14 parts of auxiliary agent, 1-6 parts of hydroxyl silicone oil and 3-7 parts of hexamethyldisilazane.
2. The method for preparing the flame-retardant ethylene propylene diene monomer rubber sleeve for the cable, which is characterized in that: the mixing process in the step (3) is as follows: heating to 60-80 deg.c and plasticating for 10-20 min.
3. The method for preparing the flame-retardant ethylene propylene diene monomer rubber sleeve for the cable, which is characterized in that: the crosslinking process in (3) is as follows: primary crosslinking: the temperature is 120-170 ℃, the time is 15-20 min, and the pressure is 10-12 Mpa; secondary crosslinking: the temperature is 210-220 ℃ and the time is 3-5 h.
4. The method for preparing the flame-retardant ethylene propylene diene monomer rubber sleeve for the cable, which is characterized in that: the cross-linking agent is dicumyl peroxide, and the auxiliary agent is one or more of 3-5 parts of zinc oxide, 2-3 parts of anti-aging agent and 3-6 parts of paraffin oil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210397247.6A CN114874556B (en) | 2022-04-15 | 2022-04-15 | Flame-retardant ethylene propylene diene monomer rubber sleeve for cable and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210397247.6A CN114874556B (en) | 2022-04-15 | 2022-04-15 | Flame-retardant ethylene propylene diene monomer rubber sleeve for cable and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114874556A CN114874556A (en) | 2022-08-09 |
| CN114874556B true CN114874556B (en) | 2023-08-25 |
Family
ID=82668758
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210397247.6A Active CN114874556B (en) | 2022-04-15 | 2022-04-15 | Flame-retardant ethylene propylene diene monomer rubber sleeve for cable and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114874556B (en) |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4101504A (en) * | 1977-04-13 | 1978-07-18 | General Electric Company | High impact compositions of a polyphenylene ether resin and alkenyl aromatic resins modified with EPDM rubber |
| JP2004149661A (en) * | 2002-10-30 | 2004-05-27 | Kuraray Co Ltd | Flame-retardant thermoplastic polymer composition |
| JP2004256715A (en) * | 2003-02-27 | 2004-09-16 | Fujikura Ltd | Molding material of epdm type rubber |
| CN1908068A (en) * | 2006-08-14 | 2007-02-07 | 上海工程技术大学 | Heat-vulcanized silicone rubber containing nano montmorillonite and preparation method thereof |
| JP2013018847A (en) * | 2011-07-08 | 2013-01-31 | Mitsubishi Cable Ind Ltd | Non-halogen flame-retardant rubber composition, and electric wire and cable using the same |
| CN103172938A (en) * | 2013-04-17 | 2013-06-26 | 西北师范大学 | Preparation method of non-halogen flame-retardant ethylene propylene diene monomer-polypropylene composite material |
| CN105018015A (en) * | 2015-08-04 | 2015-11-04 | 四川理工学院 | Method for preparing polyurethane-modified organosilicon double-component room-curing elastomer adhesive |
| CN105524381A (en) * | 2016-01-29 | 2016-04-27 | 宁波远欣石化有限公司 | Impact-resistant and high-strength plastic plate and preparation method thereof |
| WO2018130197A1 (en) * | 2017-01-13 | 2018-07-19 | 杭州星庐科技有限公司 | Rubber composite, processing method, applications, and method for manufacturing flame-retardant products |
| CN113912952A (en) * | 2021-09-30 | 2022-01-11 | 佳润科技(惠州)有限公司 | Heat-insulating rubber material and preparation method and application thereof |
| CN114284634A (en) * | 2021-12-28 | 2022-04-05 | 江苏厚生新能源科技有限公司 | Safe flame-retardant polyimide diaphragm and preparation method thereof |
-
2022
- 2022-04-15 CN CN202210397247.6A patent/CN114874556B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4101504A (en) * | 1977-04-13 | 1978-07-18 | General Electric Company | High impact compositions of a polyphenylene ether resin and alkenyl aromatic resins modified with EPDM rubber |
| JP2004149661A (en) * | 2002-10-30 | 2004-05-27 | Kuraray Co Ltd | Flame-retardant thermoplastic polymer composition |
| JP2004256715A (en) * | 2003-02-27 | 2004-09-16 | Fujikura Ltd | Molding material of epdm type rubber |
| CN1908068A (en) * | 2006-08-14 | 2007-02-07 | 上海工程技术大学 | Heat-vulcanized silicone rubber containing nano montmorillonite and preparation method thereof |
| JP2013018847A (en) * | 2011-07-08 | 2013-01-31 | Mitsubishi Cable Ind Ltd | Non-halogen flame-retardant rubber composition, and electric wire and cable using the same |
| CN103172938A (en) * | 2013-04-17 | 2013-06-26 | 西北师范大学 | Preparation method of non-halogen flame-retardant ethylene propylene diene monomer-polypropylene composite material |
| CN105018015A (en) * | 2015-08-04 | 2015-11-04 | 四川理工学院 | Method for preparing polyurethane-modified organosilicon double-component room-curing elastomer adhesive |
| CN105524381A (en) * | 2016-01-29 | 2016-04-27 | 宁波远欣石化有限公司 | Impact-resistant and high-strength plastic plate and preparation method thereof |
| WO2018130197A1 (en) * | 2017-01-13 | 2018-07-19 | 杭州星庐科技有限公司 | Rubber composite, processing method, applications, and method for manufacturing flame-retardant products |
| CN113912952A (en) * | 2021-09-30 | 2022-01-11 | 佳润科技(惠州)有限公司 | Heat-insulating rubber material and preparation method and application thereof |
| CN114284634A (en) * | 2021-12-28 | 2022-04-05 | 江苏厚生新能源科技有限公司 | Safe flame-retardant polyimide diaphragm and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114874556A (en) | 2022-08-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110335711B (en) | Rat-proof and ant-proof low-smoke halogen-free flame-retardant control cable for ships | |
| WO2021085819A1 (en) | Decrosslinked polyolefin resin, and resin composition comprising same | |
| CN111647218A (en) | Ultra-soft low-smoke halogen-free flame-retardant polyolefin cable material and preparation method thereof | |
| CN114874556B (en) | Flame-retardant ethylene propylene diene monomer rubber sleeve for cable and preparation method thereof | |
| CN116987349A (en) | Halogen-free flame-retardant cable material for aluminum alloy cable | |
| CN115160575B (en) | Flame-retardant ethylene propylene diene monomer rubber and preparation method thereof | |
| CN110551356B (en) | Flame-retardant sheath material for ultrahigh-voltage cable and preparation method thereof | |
| WO2016163765A1 (en) | Decrosslinked polyolefin resin and resin composition containing same | |
| CN114213707B (en) | Intumescent flame retardant, preparation method and application thereof | |
| CN114231036B (en) | High-strength synergistic flame-retardant room temperature vulcanized silicone rubber and preparation method thereof | |
| CN114106340A (en) | Organic silicon hybrid melamine cyanurate, and preparation method and application thereof | |
| CN111073298A (en) | Flame-retardant plugging agent for substation and preparation method and use method thereof | |
| CN117070018A (en) | Micro-crosslinking halogen-free flame-retardant modified ethylene-vinyl acetate copolymer cable material and preparation method thereof | |
| CN111647264A (en) | High-flame-retardant low-smoke halogen-free TPU cable material and preparation method thereof | |
| CN117316512B (en) | Silicon rubber high-temperature-resistant cable and preparation method thereof | |
| KR20040076435A (en) | Self-extinguishing additive RTV silicone rubber composition | |
| CN112574576B (en) | Polymer foam material and preparation method thereof | |
| CN116102823B (en) | Flame-retardant EPDM (ethylene-propylene-diene monomer) rubber material with shape self-recovery function and preparation method thereof | |
| JP3909146B2 (en) | Manufacturing method of rubber products | |
| CN115477827B (en) | Preparation method and application of phosphorus-nitrogen-silicon composite intumescent flame retardant | |
| CN115594979B (en) | Flame-retardant and tracking-resistant silicone rubber composition and preparation method and application thereof | |
| KR100758316B1 (en) | Self-extinguishing additive RTV-2 silicone rubber composition | |
| CN115895290A (en) | Fluororubber composition and preparation method and application thereof | |
| CN116656296A (en) | High-temperature-resistant packaging adhesive for electronic components and manufacturing process thereof | |
| CN117316512A (en) | Silicon rubber high-temperature-resistant cable and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |