CN111524652B - Ethylene propylene rubber insulation rat-proof ant-proof low-smoke halogen-free flame-retardant power cable for ships - Google Patents
Ethylene propylene rubber insulation rat-proof ant-proof low-smoke halogen-free flame-retardant power cable for ships Download PDFInfo
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- CN111524652B CN111524652B CN202010344320.4A CN202010344320A CN111524652B CN 111524652 B CN111524652 B CN 111524652B CN 202010344320 A CN202010344320 A CN 202010344320A CN 111524652 B CN111524652 B CN 111524652B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B9/00—Power cables
- H01B9/02—Power cables with screens or conductive layers, e.g. for avoiding large potential gradients
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
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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
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/02—Disposition of insulation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
- H01B7/18—Protection against damage caused by wear, mechanical force or pressure; Sheaths; Armouring
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
- H01B7/29—Protection against damage caused by extremes of temperature or by flame
- H01B7/295—Protection against damage caused by extremes of temperature or by flame using material resistant to flame
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
Abstract
The invention relates to an ethylene propylene rubber insulated rat-proof ant-proof low-smoke halogen-free flame-retardant power cable for ships, which comprises an insulated wire core, a halogen-free flame-retardant belt and a sheath layer, wherein the sheath layer comprises the following raw materials in parts by weight: 30-70 parts of ethylene propylene diene monomer, 30-70 parts of EVA (ethylene-vinyl acetate copolymer), 4-7 parts of organic montmorillonite, 3-4.5 parts of crosslinking agent DCP, 2-4 parts of crosslinking assistant, 45-75 parts of halogen-free expansion flame-retardant material, 0.4-0.8 part of anti-aging agent, 0.15-0.3 part of ultraviolet absorbent, 7.5-15 parts of modifier and 1.5-3 parts of rat and termite proofing agent. Compared with the prior art, the invention not only can meet the electrical performance and mechanical performance indexes specified by the national standard and meet the flame retardant performance required by GB/T19666A bundled combustion tests, but also has the functions of rat and ant prevention; in addition, the oxygen index of the sheath exceeds 38, the smoke generated during combustion is small, and the light transmittance reaches 75-95%.
Description
Technical Field
The invention relates to the technical field, in particular to an ethylene propylene rubber insulated rat-proof ant-proof low-smoke halogen-free flame-retardant power cable for ships.
Background
The power cable for the ship is an electrical product for transmitting power on naval ships, is a 'blood vessel' of the ship, is generally connected with important electrical equipment such as a main distribution board, a distribution box and the like, and implements sectional connection between a generator set and the electrical equipment of the whole ship. The device has wide application range and large using amount, is a basic guarantee for normal operation of a ship power system and electrical equipment, and has great influence on ensuring power supply of important equipment, personnel safety, fire safety and the like.
In recent years, equipment for constructing ships, warships and the like is increased in China so as to strengthen the defense force of navy. Correspondingly, the demand of ship cables as a supporting industry is increased. With the technical innovation and development of equipment such as large-scale long-range ships, ships and warships and the like, new requirements are put forward on the functions of a cable wiring system, namely, the requirements of safety, environmental protection, rat and ant prevention and the like are met, but the existing cable cannot meet the performance requirements.
Disclosure of Invention
In order to solve the technical problems, the invention provides an ethylene propylene rubber insulated rat-proof and termite-proof low-smoke halogen-free flame-retardant power cable for ships, which meets the requirements of safety, environmental protection and rat and termite resistance.
The technical problem to be solved by the invention is realized by adopting the following technical scheme:
the utility model provides a naval vessel is with insulating protection against rodents of ethylene-propylene rubber rat-proof low smoke and zero halogen flame retardant power cable, includes insulating core, halogen-free flame retardant band and restrictive coating, insulating core includes the conductor and crowded package insulating layer outside the conductor, the insulating layer adopts ethylene-propylene-diene monomer to glue as the blend of base stock, insulating core is outer around having wrapped there is halogen-free flame retardant band, copper wire or tinned copper wire shielding layer are woven to halogen-free flame retardant outband, the restrictive coating outsourcing is outside the shielding layer, the raw materials of restrictive coating include according to part by weight:
30-70 parts of ethylene propylene diene monomer, 30-70 parts of EVA (ethylene-vinyl acetate copolymer), 4-7 parts of organic montmorillonite, 3-4.5 parts of crosslinking agent DCP, 2-4 parts of crosslinking assistant, 45-75 parts of halogen-free expansion flame-retardant material, 0.4-0.8 part of anti-aging agent, 0.15-0.3 part of ultraviolet absorbent, 7.5-15 parts of modifier and 1.5-3 parts of rat and termite proofing agent.
Further, the organic montmorillonite comprises the following components in parts by weight:
montmorillonite, deionized water and 20% dioctyl dimethyl ammonium bromide aqueous solution, wherein the corresponding weight ratio is 1:25-30: 4.5-5.
Further, the preparation process of the organic montmorillonite is as follows:
adding montmorillonite and deionized water, heating to 65-75 ℃, and dropwise adding a 20% dioctyl dimethyl ammonium bromide aqueous solution;
secondly, processing for 6-8 minutes by microwave equipment every 35-55 minutes;
after 4-5 hours, the precipitate was washed with deionized water, dried to constant weight under vacuum, then ground and sieved through a 500 mesh sieve.
Further, the crosslinking assistant comprises the following components in parts by weight:
accelerator TATC and accelerator CZ, the corresponding weight ratio is 1: 0.3-0.5.
Further, the halogen-free intumescent flame retardant material comprises the following components in parts by weight:
ammonium polyphosphate, melamine polyphosphate, expanded graphite and dinonyl acid phosphate in the weight ratio of 1 to 0.15-0.3 to 0.05-0.2.
Further, the manufacturing process of the halogen-free intumescent flame retardant material is as follows:
(A) mixing and stirring 1 mol of isononyl alcohol and 0.3-0.6 mol of n-hexane at the reaction temperature of about 8-12 ℃, and then dropwise adding a mixed solution of 1 mol of phosphorus oxychloride and 0.4-0.6 mol of n-hexane;
(B) heating to 35 deg.C, stirring for 40 min, continuing to heat to 55 deg.C, stirring for 45 min, heating to 70-75 deg.C, reacting at 70-75 deg.C until no hydrogen chloride gas is discharged, and discharging unreacted isononyl alcohol and phosphorus oxychloride;
(C) dropwise adding 1.5-2 mol of water, keeping the temperature at 55 ℃ for 1 hour, and washing hydrogen chloride by using distilled water to obtain dinonyl acid phosphate;
(D) uniformly mixing ammonium polyphosphate, melamine polyphosphate, expanded graphite and dinonyl acid phosphate at the temperature of 90-110 ℃, then heating to the temperature of 160-170 ℃ and preserving the heat for 50-70 minutes to obtain the halogen-free expanded flame-retardant material.
Further, the anti-aging agent comprises the following components in parts by weight:
4, 4' -thiobis (6-tert-butyl-3-methylphenol) and tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester in a corresponding weight ratio of 1: 1-2.
The ultraviolet absorbent comprises the following components in parts by weight:
salicylic acid bisphenol A ester, 2-hydroxy-4-n-octyloxy-benzophenone and 2, 4-dihydroxy benzophenone in a weight ratio of 1:05-0.8: 0.3-0.5.
Further, the modifier comprises the following components in parts by weight:
pentaerythritol and melamine in a weight ratio of 1: 3-8.
Further, the rat repellent and the termite repellent comprise the following components in parts by weight:
the capsaicin environment-friendly ratproof agent and the cypermethrin low-toxicity termiticide with the corresponding weight ratio of 1: 0.5-0.8.
The invention has the beneficial effects that:
compared with the prior art, the invention not only can meet the electrical performance and mechanical performance indexes specified by the national standard and meet the flame retardant performance required by GB/T19666A bundled combustion test, but also has the functions of rat and ant prevention; in addition, the oxygen index of the sheath exceeds 38, the smoke generated during combustion is small, and the light transmittance reaches 75-95%.
Drawings
The invention is further illustrated with reference to the following figures and examples:
FIG. 1 is a schematic structural diagram of the present invention.
Detailed Description
In order to make the technical means, the creation features, the achievement purposes and the effects of the invention easy to understand, the invention is further explained in the following with the accompanying drawings and the embodiments.
The first embodiment is as follows:
as shown in fig. 1, a naval vessel is with ethylene-propylene rubber insulation protection against rodents protection against ants low smoke and zero halogen flame retardant power cable, including insulation core, halogen-free flame retardant belt 3 and restrictive coating 5, insulation core includes conductor 1 and crowded package insulating layer 2 outside conductor 1, insulating layer 2 adopts ethylene-propylene-diene rubber to glue the mixture as the base stock, insulation core has halogen-free flame retardant belt 3 around the package outward, copper wire or tinned copper wire shielding layer 4 are woven outward to halogen-free flame retardant belt 3, restrictive coating 5 outsourcing is outside at shielding layer 4, restrictive coating 5's raw materials include according to part by weight:
70 parts of ethylene propylene diene monomer, 30 parts of EVA (ethylene-vinyl acetate copolymer), 7 parts of organic montmorillonite, 3 parts of a crosslinking agent DCP (DCP), 4 parts of a crosslinking aid, 45 parts of a halogen-free expansion flame-retardant material, 0.8 part of an anti-aging agent, 0.15 part of an ultraviolet absorbent, 15 parts of a modifier, and 1.5 parts of a rat repellent and a termite repellent.
In order to improve the flame retardant property and the mechanical property of the cable, the invention uses organic montmorillonite treated by microwave and prepares the organic montmorillonite by adopting a microwave radiation method.
Wherein the organic montmorillonite comprises the following components in parts by weight:
montmorillonite, deionized water and a 20% dioctyl dimethyl ammonium bromide aqueous solution, wherein the corresponding weight ratio is 1:25: 5.
The specific method comprises the following steps:
montmorillonite and deionized water are added, the mixture is heated to 65 ℃, and aqueous solution of 20 percent dioctyl dimethyl ammonium bromide is dripped.
(II) treating for 6 minutes by using microwave equipment every 55 minutes; wherein the microwave device is capable of hundreds of millions of vibrations per second.
After stirring for 5 hours, the precipitate was filtered off with suction and washed with deionized water, dried to constant weight under vacuum, then ground and sieved through a 500-mesh sieve.
Wherein the crosslinking assistant comprises the following components in parts by weight:
accelerator TATC and accelerator CZ, and the corresponding weight ratio is 1: 0.3.
Ethylene propylene diene monomer and EVA are mixed according to a certain proportion to be used as framework materials, and expanded flame-retardant materials such as ammonium polyphosphate, melamine polyphosphate, expanded graphite, dinonyl acid phosphate and the like are adopted, so that the material has good mechanical properties, the carbon forming rate of material combustion is increased, and the flame-retardant property is improved.
The halogen-free intumescent flame retardant material comprises the following components in parts by weight:
ammonium polyphosphate, melamine polyphosphate, expanded graphite and dinonyl acid phosphate, wherein the corresponding weight ratio is 1:0.15:0.2: 0.05.
Before the preparation of the halogen-free intumescent flame retardant material, an acid type dinonyl phosphate coupling agent needs to be synthesized, and the preparation process of the acid type dinonyl phosphate coupling agent is as follows:
(A) mixing and stirring 1 mole of isononanol and 0.3 mole of n-hexane at the reaction temperature of about 12 ℃, and then dropwise adding a mixed solution of 1 mole of phosphorus oxychloride and 0.4 mole of n-hexane;
(B) heating to 35 ℃, stirring for 40 minutes, continuously heating to 55 ℃, stirring for 45 minutes, heating to 70 ℃, keeping the temperature at 70 ℃ for reaction until no hydrogen chloride gas is discharged and unreacted isononyl alcohol and phosphorus oxychloride are discharged;
(C) then, 1.5 mol of water was added dropwise, and after heat preservation at 55 ℃ for 1 hour, hydrogen chloride was washed with distilled water to obtain dinonyl acid phosphate.
After the acid phosphoric acid dinonyl ester coupling agent is obtained, ammonium polyphosphate, melamine polyphosphate, expanded graphite and acid phosphoric acid dinonyl ester are uniformly mixed at the temperature of 90 ℃, and then heated to 170 ℃ and kept for 50 minutes to obtain the halogen-free expanded flame-retardant material.
The anti-aging agent comprises the following components in parts by weight:
4, 4' -thiobis (6-tert-butyl-3-methylphenol), tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester in a corresponding weight ratio of 1:1.
The ultraviolet absorbent comprises the following components in parts by weight:
salicylic acid bisphenol A ester, 2-hydroxy-4-n-octyloxy-benzophenone and 2, 4-dihydroxy benzophenone in a weight ratio of 1:0.5: 0.5.
The modifier comprises the following components in parts by weight:
pentaerythritol and melamine in a corresponding weight ratio of 1: 3.
The rat-proof agent and the termite-proof agent comprise the following components in parts by weight:
the capsaicin environment-friendly ratproof agent and the cypermethrin low-toxicity termiticide with the corresponding weight ratio of 1: 0.8.
After the components of the components are obtained, ethylene propylene diene monomer, EVA, organic montmorillonite, a crosslinking agent, a crosslinking auxiliary agent, a halogen-free intumescent flame retardant material, an anti-aging agent, an ultraviolet absorbent, a modifier, a rat repellent and an ant repellent are mixed, milled and rolled out to form strips in an internal mixer at 90 ℃ to produce a sheath material, and then the sheath material is extruded and vulcanized by a continuous vulcanizing machine to obtain the sheath layer 5.
Example two:
the difference from the first embodiment is that,
50 parts of ethylene propylene diene monomer, 50 parts of EVA (ethylene-vinyl acetate copolymer), 5.5 parts of organic montmorillonite, 3.75 parts of a crosslinking agent DCP (DCP), 3 parts of a crosslinking assistant, 60 parts of a halogen-free intumescent flame retardant material, 0.6 part of an anti-aging agent, 0.225 part of an ultraviolet absorbent, 11.25 parts of a modifier, and 2.25 parts of a ratproof agent and a termiticide.
Wherein the organic montmorillonite comprises the following components in parts by weight:
montmorillonite, deionized water and a 20% dioctyl dimethyl ammonium bromide aqueous solution, wherein the corresponding weight ratio is 1:30: 4.5.
The specific method comprises the following steps:
montmorillonite and deionized water are added, the mixture is heated to 75 ℃, and aqueous solution of 20 percent dioctyl dimethyl ammonium bromide is dripped.
(II) treating for 8 minutes by using microwave equipment every 55 minutes; wherein the microwave device is capable of hundreds of millions of vibrations per second.
After stirring for 4 hours, the precipitate was filtered off with suction and washed with deionized water, dried to constant weight under vacuum, then ground and sieved through a 500-mesh sieve.
Wherein the crosslinking assistant comprises the following components in parts by weight:
accelerator TATC and accelerator CZ, and the corresponding weight ratio is 1: 0.5.
The halogen-free intumescent flame retardant material comprises the following components in parts by weight:
ammonium polyphosphate, melamine polyphosphate, expanded graphite and dinonyl acid phosphate, wherein the corresponding weight ratio is 1:0.3:0.05: 0.2.
Before the preparation of the halogen-free intumescent flame retardant material, an acid type dinonyl phosphate coupling agent needs to be synthesized, and the preparation process of the acid type dinonyl phosphate coupling agent is as follows:
(A) mixing and stirring 1 mole of isononanol and 0.6 mole of n-hexane at the reaction temperature of about 8 ℃, and then dropwise adding a mixed solution of 1 mole of phosphorus oxychloride and 0.6 mole of n-hexane;
(B) heating to 35 ℃, stirring for 40 minutes, continuously heating to 55 ℃, stirring for 45 minutes, heating to 75 ℃, keeping the temperature at 75 ℃ for reaction until no hydrogen chloride gas is discharged and unreacted isononyl alcohol and phosphorus oxychloride are discharged;
(C) then 2 mol of water is added dropwise, after heat preservation is carried out for 1 hour at 55 ℃, the hydrogen chloride is washed by distilled water, and the dinonyl acid phosphate is obtained.
After the acid phosphoric acid dinonyl ester coupling agent is obtained, ammonium polyphosphate, melamine polyphosphate, expanded graphite and acid phosphoric acid dinonyl ester are uniformly mixed at the temperature of 110 ℃, and then heated to 160 ℃ and kept warm for 70 minutes to obtain the halogen-free expanded flame-retardant material.
The anti-aging agent comprises the following components in parts by weight:
4, 4' -thiobis (6-tert-butyl-3-methylphenol), tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester in a corresponding weight ratio of 1: 2.
The ultraviolet absorbent comprises the following components in parts by weight:
salicylic acid bisphenol A ester, 2-hydroxy-4-n-octyloxy-benzophenone and 2, 4-dihydroxy benzophenone in a corresponding weight ratio of 1:0.8: 0.3.
The modifier comprises the following components in parts by weight:
pentaerythritol and melamine in a weight ratio of 1: 8.
The rat-proof agent and the termite-proof agent comprise the following components in parts by weight:
the capsaicin environment-friendly ratproof agent and the cypermethrin low-toxicity termiticide with the corresponding weight ratio of 1: 0.5.
Example three:
the difference between the first and the second embodiments is that,
40 parts of ethylene propylene diene monomer, 60 parts of EVA (ethylene-vinyl acetate copolymer), 5 parts of organic montmorillonite, 3.5 parts of a crosslinking agent DCP (DCP), 2.5 parts of a crosslinking assistant, 50 parts of a halogen-free expansion flame-retardant material, 0.5 part of an anti-aging agent, 0.2 part of an ultraviolet absorbent, 10 parts of a modifier, and 2 parts of a rat repellent and a termite repellent.
Wherein the organic montmorillonite comprises the following components in parts by weight:
montmorillonite, deionized water and a 20% dioctyl dimethyl ammonium bromide aqueous solution, wherein the corresponding weight ratio is 1:28: 4.8.
The specific method comprises the following steps:
montmorillonite and deionized water are added, the mixture is heated to 70 ℃, and aqueous solution of 20 percent dioctyl dimethyl ammonium bromide is dripped.
(II) processing for 7 minutes by using microwave equipment every 45 minutes; wherein the microwave device is capable of hundreds of millions of vibrations per second.
After stirring for 4.5 hours, the precipitate was filtered off with suction and washed with deionized water, dried to constant weight under vacuum, then ground and sieved through a 500-mesh sieve.
Wherein the crosslinking assistant comprises the following components in parts by weight:
accelerator TATC and accelerator CZ, and the corresponding weight ratio is 1: 0.4.
The halogen-free intumescent flame retardant material comprises the following components in parts by weight:
ammonium polyphosphate, melamine polyphosphate, expanded graphite and dinonyl acid phosphate in a weight ratio of 1:0.23:0.13: 0.13.
Before the preparation of the halogen-free intumescent flame retardant material, an acid type dinonyl phosphate coupling agent needs to be synthesized, and the preparation process of the acid type dinonyl phosphate coupling agent is as follows:
(A) mixing and stirring 1 mole of isononanol and 0.45 mole of n-hexane at the reaction temperature of about 10 ℃, and then dropwise adding a mixed solution of 1 mole of phosphorus oxychloride and 0.5 mole of n-hexane;
(B) heating to 35 ℃, stirring for 40 minutes, continuously heating to 55 ℃, stirring for 45 minutes, heating to 73 ℃, keeping the temperature at 73 ℃ for reaction until no hydrogen chloride gas is discharged and unreacted isononyl alcohol and phosphorus oxychloride are discharged;
(C) then, 1.8 mol of water was added dropwise, and after heat preservation at 55 ℃ for 1 hour, hydrogen chloride was washed with distilled water to obtain dinonyl acid phosphate.
After the acid dinonyl phosphate coupling agent is obtained, uniformly mixing ammonium polyphosphate, melamine polyphosphate, expanded graphite and acid dinonyl phosphate at the temperature of 100 ℃, heating to 165 ℃ and preserving heat for 60 minutes to obtain the halogen-free expanded flame-retardant material.
The anti-aging agent comprises the following components in parts by weight:
4, 4' -thiobis (6-tert-butyl-3-methylphenol) and tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester in a corresponding weight ratio of 1: 1.5.
The ultraviolet absorbent comprises the following components in parts by weight:
salicylic acid bisphenol A ester, 2-hydroxy-4-n-octyloxy-benzophenone and 2, 4-dihydroxy benzophenone in a corresponding weight ratio of 1:0.7: 0.4.
The modifier comprises the following components in parts by weight:
pentaerythritol and melamine in a weight ratio of 1: 5.5.
The rat-proof agent and the termite-proof agent comprise the following components in parts by weight:
the capsaicin environment-friendly ratproof agent and the cypermethrin low-toxicity termiticide with the corresponding weight ratio of 1: 0.65.
Example four:
the difference from the first, second and third embodiments is that,
55 parts of ethylene propylene diene monomer, 45 parts of EVA (ethylene-vinyl acetate copolymer), 6 parts of organic montmorillonite, 4 parts of a crosslinking agent DCP (DCP), 2.8 parts of a crosslinking aid, 55 parts of a halogen-free expansion flame-retardant material, 0.65 part of an anti-aging agent, 0.25 part of an ultraviolet absorbent, 12.5 parts of a modifier, and 2.5 parts of a rat repellent and a termite repellent.
Wherein the organic montmorillonite comprises the following components in parts by weight:
montmorillonite, deionized water and a 20% dioctyl dimethyl ammonium bromide aqueous solution, wherein the corresponding weight ratio is 1:27: 4.7.
The specific method comprises the following steps:
montmorillonite and deionized water are added, the mixture is heated to 72 ℃, and aqueous solution of 20 percent dioctyl dimethyl ammonium bromide is dripped.
(II) treating for 7.5 minutes by using a microwave device every 50 minutes; wherein the microwave device is capable of hundreds of millions of vibrations per second.
After stirring for 4.7 hours, the precipitate was filtered off with suction and washed with deionized water, dried to constant weight under vacuum, then ground and sieved through a 500-mesh sieve.
Wherein the crosslinking assistant comprises the following components in parts by weight:
accelerator TATC and accelerator CZ, and the corresponding weight ratio is 1: 0.45.
The halogen-free intumescent flame retardant material comprises the following components in parts by weight:
ammonium polyphosphate, melamine polyphosphate, expanded graphite and dinonyl acid phosphate in a weight ratio of 1:0.22:0.12: 0.12.
Before the preparation of the halogen-free intumescent flame retardant material, an acid type dinonyl phosphate coupling agent needs to be synthesized, and the preparation process of the acid type dinonyl phosphate coupling agent is as follows:
(A) mixing and stirring 1 mole of isononanol and 0.5 mole of n-hexane at the reaction temperature of about 11 ℃, and then dropwise adding a mixed solution of 1 mole of phosphorus oxychloride and 0.55 mole of n-hexane;
(B) heating to 35 ℃, stirring for 40 minutes, continuously heating to 55 ℃, stirring for 45 minutes, heating to 72 ℃, keeping the temperature at 72 ℃ for reaction until no hydrogen chloride gas is discharged and unreacted isononyl alcohol and phosphorus oxychloride are discharged;
(C) then, 1.7 mol of water was added dropwise, and after heat preservation at 55 ℃ for 1 hour, hydrogen chloride was washed with distilled water to obtain dinonyl acid phosphate.
After the acid phosphoric acid dinonyl ester coupling agent is obtained, ammonium polyphosphate, melamine polyphosphate, expanded graphite and acid phosphoric acid dinonyl ester are uniformly mixed at the temperature of 105 ℃, and then heated to 168 ℃ and kept for 65 minutes to obtain the halogen-free expanded flame-retardant material.
The anti-aging agent comprises the following components in parts by weight:
4, 4' -thiobis (6-tert-butyl-3-methylphenol) and tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester in a corresponding weight ratio of 1: 1.8.
The ultraviolet absorbent comprises the following components in parts by weight:
salicylic acid bisphenol A ester, 2-hydroxy-4-n-octyloxy-benzophenone and 2, 4-dihydroxy benzophenone in a corresponding weight ratio of 1:0.6: 0.35.
The modifier comprises the following components in parts by weight:
pentaerythritol and melamine in a weight ratio of 1: 6.5.
The rat-proof agent and the termite-proof agent comprise the following components in parts by weight:
the capsaicin environment-friendly ratproof agent and the cypermethrin low-toxicity termiticide with the corresponding weight ratio of 1: 0.7.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (1)
1. The utility model provides a naval vessel is with insulating protection against rodents of ethylene-propylene rubber rat-proof low smoke and zero halogen flame retardant power cable, includes insulation core, halogen-free flame retardant band (3) and restrictive coating (5), and insulation core includes conductor (1) and crowded package insulating layer (2) outside conductor (1), insulating layer (2) adopt ethylene-propylene-diene rubber to be the mixed glue of base stock, insulation core is around there being halogen-free flame retardant band (3) outward, there is not halogen-free flame retardant band (3) to weave copper wire or tinned copper wire shielding layer (4) outward, restrictive coating (5) outsourcing is in shielding layer (4) outside, its characterized in that: the sheath layer (5) comprises the following raw materials in parts by weight:
30-70 parts of ethylene propylene diene monomer, 30-70 parts of EVA (ethylene-vinyl acetate), 4-7 parts of organic montmorillonite, 3-4.5 parts of crosslinking agent DCP (DCP), 2-4 parts of crosslinking assistant, 45-75 parts of halogen-free expansion flame-retardant material, 0.4-0.8 part of anti-aging agent, 0.15-0.3 part of ultraviolet absorbent, 7.5-15 parts of modifier, and 1.5-3 parts of rat proofing agent and termite proofing agent;
the organic montmorillonite comprises the following components in parts by weight:
montmorillonite, deionized water and a 20% dioctyl dimethyl ammonium bromide aqueous solution, wherein the corresponding weight ratio is 1:25-30: 4.5-5;
the preparation process of the organic montmorillonite is as follows:
adding montmorillonite and deionized water, heating to 65-75 ℃, and dropwise adding a 20% dioctyl dimethyl ammonium bromide aqueous solution;
secondly, processing for 6-8 minutes by microwave equipment every 35-55 minutes;
(III) after 4-5 hours, washing the precipitate with deionized water, drying to constant weight in a vacuum environment, then grinding and sieving by a 500-mesh sieve;
the crosslinking assistant comprises the following components in parts by weight:
accelerator TATC and accelerator CZ, the corresponding weight ratio is 1: 0.3-0.5;
the halogen-free intumescent flame retardant material comprises the following components in parts by weight:
ammonium polyphosphate, melamine polyphosphate, expanded graphite and dinonyl acid phosphate in the weight ratio of 1 to 0.15-0.3 to 0.05-0.2;
the preparation process of the halogen-free intumescent flame retardant material is as follows:
(A) mixing and stirring 1 mol of isononyl alcohol and 0.3-0.6 mol of n-hexane at the reaction temperature of 8-12 ℃, and then dropwise adding a mixed solution of 1 mol of phosphorus oxychloride and 0.4-0.6 mol of n-hexane;
(B) heating to 35 deg.C, stirring for 40 min, continuing to heat to 55 deg.C, stirring for 45 min, heating to 70-75 deg.C, reacting at 70-75 deg.C until no hydrogen chloride gas is discharged, and discharging unreacted isononyl alcohol and phosphorus oxychloride;
(C) dropwise adding 1.5-2 mol of water, keeping the temperature at 55 ℃ for 1 hour, and washing hydrogen chloride by using distilled water to obtain dinonyl acid phosphate;
(D) uniformly mixing ammonium polyphosphate, melamine polyphosphate, expanded graphite and dinonyl acid phosphate at the temperature of 90-110 ℃, heating to the temperature of 160-170 ℃ and preserving the heat for 50-70 minutes to obtain a halogen-free expanded flame-retardant material;
the anti-aging agent comprises the following components in parts by weight:
4, 4' -thiobis (6-tert-butyl-3-methylphenol), tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester in a corresponding weight ratio of 1: 1-2;
the ultraviolet absorbent comprises the following components in parts by weight:
salicylic acid bisphenol A ester, 2-hydroxy-4-n-octyloxy-benzophenone and 2, 4-dihydroxy benzophenone in a weight ratio of 1:05-0.8: 0.3-0.5;
the modifier comprises the following components in parts by weight:
pentaerythritol and melamine in a corresponding weight ratio of 1: 3-8;
the rat-proof agent and the termite-proof agent comprise the following components in parts by weight:
the capsaicin environment-friendly ratproof agent and the cypermethrin low-toxicity termiticide with the corresponding weight ratio of 1: 0.5-0.8.
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| CN202010344320.4A CN111524652B (en) | 2020-04-27 | 2020-04-27 | Ethylene propylene rubber insulation rat-proof ant-proof low-smoke halogen-free flame-retardant power cable for ships |
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| CN202010344320.4A CN111524652B (en) | 2020-04-27 | 2020-04-27 | Ethylene propylene rubber insulation rat-proof ant-proof low-smoke halogen-free flame-retardant power cable for ships |
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| CN113936850A (en) * | 2021-10-22 | 2022-01-14 | 曲阜市虹飞电缆有限公司 | Effectual fire-retardant type power cable of resistance to compression |
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| US8173255B2 (en) * | 2010-01-07 | 2012-05-08 | King Abdulaziz City Science And Technology | Clean flame retardant insulation composition to enhance mechanical properties and flame retardancy for wire and cable |
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Denomination of invention: A low-smoke halogen-free flame-retardant power cable with ethylene-propylene rubber insulation for ships Effective date of registration: 20220919 Granted publication date: 20210907 Pledgee: Gaogou Branch of Anhui Wuwei Rural Commercial Bank Co.,Ltd. Pledgor: ANHUI HUANENG CABLE GROUP Co.,Ltd. Registration number: Y2022980015663 |
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