CN111117136A - Cable material - Google Patents

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Publication number
CN111117136A
CN111117136A CN201911375709.9A CN201911375709A CN111117136A CN 111117136 A CN111117136 A CN 111117136A CN 201911375709 A CN201911375709 A CN 201911375709A CN 111117136 A CN111117136 A CN 111117136A
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parts
cable material
mixture
flame retardant
stirring
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CN111117136B (en
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刘建平
宋霞
刘子赫
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Wenzhou University
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Wenzhou University
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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
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
    • C07F7/0814—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring said ring is substituted at a C ring atom by Si
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
    • C07F7/083—Syntheses without formation of a Si-C bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Organic Insulating Materials (AREA)

Abstract

The invention discloses a cable material, which is prepared by taking modified polyethylene and ethylene propylene diene monomer as base materials and adding auxiliary agents such as a flame retardant, a stabilizer, an anti-aging agent and the like for reaction; the modified polyethylene is prepared by taking polyethylene as a raw material, tert-butyl peroxymaleate as an initiator, sodium dodecyl benzene sulfonate as a catalyst and adding a modifier; the modifier is selected from a mixture of vinyl trimethoxy silane, 2, 3-bis (2,4, 5-trimethyl-3-thiophene) maleic anhydride and (3,3, 3-trifluoropropyl) trimethoxy silane; the flame retardant is a mixture of 6- (difluoromethoxy) -2- (trimethylsilyl) benzo [4,5] imidazo [2,1-b ] thiazole, 10- (2, 5-dihydroxyphenyl) -10-hydrogen-9-oxa-10-phosphaphenanthrene-10-oxide and triphenyl antimony oxide; the finally prepared cable material has high tensile strength and elongation at break, high flame retardant property and high tensile strength and elongation at break even after thermal aging and sunlight aging treatment.

Description

Cable material
Technical Field
The invention relates to the technical field of novel cable materials, in particular to a cable material.
Background
The plastic used for the insulation and the sheath of the electric wire and the electric cable is commonly called as a cable material and comprises various varieties of rubber, plastic, nylon and the like. The polyethylene cable material has the outstanding performance characteristics of light weight, good mechanical property, good low-temperature resistance, good environmental stress cracking resistance, good processability and the like, and is widely applied in the field of electric wires and cables, so the polyethylene cable material is one of the indispensable important components in the cable material.
With the rapid development of science and technology, people have higher and higher requirements on the performance of cable materials, and in order to improve the safety, people add a proper amount of flame retardant into polyethylene to improve the flame retardant performance of polyethylene cable materials. At present, most of flame retardants added into polyethylene are inorganic flame retardants, such as aluminum hydroxide, magnesium hydroxide and the like, and although the flame retardant performance of the polyethylene cable material can be improved by adding the inorganic flame retardants, the tensile strength and the elongation at break of the polyethylene cable material can be reduced to a certain extent, so that the application range of the cable material is limited.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a cable material which has strong flame retardant property, and also has high tensile strength and elongation at break.
In order to achieve the purpose, the invention provides the following technical scheme: a cable material comprises the following substances in parts by weight:
70-80 parts of modified polyethylene;
20-30 minutes of ethylene propylene diene monomer;
10-15 parts of a flame retardant;
5-10 parts of a plasticizer;
2-4 parts of a stabilizer;
2-4 parts of an anti-aging agent;
1-2 parts of a lubricant;
3-5 parts of a filler.
As a further improvement of the invention, the modified polyethylene comprises the following substances in parts by weight:
60 parts of polyethylene;
2 parts of tert-butyl peroxymaleate;
3 parts of sodium dodecyl benzene sulfonate;
2 parts of dimethylamino propyl methacryl;
2 parts of styrene;
7 parts of a modifier;
the modifier is a mixture of vinyl trimethoxy silane, 2, 3-bis (2,4, 5-trimethyl-3-thiophene) maleic anhydride and (3,3, 3-trifluoropropyl) trimethoxy silane, and the mass ratio of the modifier to the (3,3, 3-trifluoropropyl) trimethoxy silane is 1:1: 1.
As a further improvement of the invention, the preparation method of the modified polyethylene comprises the following steps:
the method comprises the following steps: weighing the required materials according to the set weight parts, adding polyethylene, tert-butyl peroxymaleate, sodium dodecyl benzene sulfonate, dimethylaminopropyl methacrylyl and styrene into a reaction vessel filled with acetone, stirring and mixing, uniformly mixing, and reacting at the temperature of 60-80 ℃ for 30-40min under the protection of nitrogen;
step two: adding the modifier into a reaction vessel for continuous reaction, and reacting for 2-3h at the temperature of 80-100 ℃; filtering, purifying and drying after the reaction is finished to prepare the modified polyethylene.
As a further improvement of the invention, the flame retardant is a mixture of 6- (difluoromethoxy) -2- (trimethylsilyl) benzo [4,5] imidazo [2,1-b ] thiazole, 10- (2, 5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide and triphenylantimony oxide in a mass ratio of 2:3: 1;
wherein 6- (difluoromethoxy) -2- (trimethylsilyl) benzo [4,5]]Imidazo [2,1-b ]]The structural formula of the thiazole is
Figure BDA0002340900050000031
The structural formula of the 10- (2, 5-dihydroxyphenyl) -10-hydrogen-9-oxa-10-phosphaphenanthrene-10-oxide is shown in the specification
Figure BDA0002340900050000032
The structural formula of the triphenyl antimony oxide is shown as
Figure BDA0002340900050000033
As a further improvement of the invention, the preparation method of the 6- (difluoromethoxy) -2- (trimethylsilyl) benzo [4,5] imidazo [2,1-b ] thiazole comprises the following steps:
putting trimethyl acetylene silicon, 5-difluoromethoxy-2-mercapto-1H-benzimidazole, a copper catalyst, a ligand, an oxidant and an alkaline substance into a reaction vessel filled with a solvent, and stirring and mixing; after being mixed evenly, the mixture reacts for 18 to 22 hours at the temperature of 60 to 80 ℃ to prepare 6- (difluoromethoxy) -2- (trimethylsilyl) benzo [4,5] imidazo [2,1-b ] thiazole;
the reaction formula is as follows:
Figure BDA0002340900050000041
as a further improvement of the present invention, the copper catalyst is copper fluoride;
the ligand is 2, 9-diisopropyl-1, 10-phenanthroline;
the oxidant is iodine simple substance;
the alkaline substance is cesium carbonate;
the solvent is toluene.
As a further improvement of the invention, the stabilizer is a mixture of bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate, 1, 2-epoxy-4-vinylcyclohexane and tributyl ethylene tin in a mass ratio of 2:1: 1.
As a further improvement of the invention, the anti-aging agent is a mixture of (R) -N-epoxypropylphthalimide, 1-benzhydrylazetidin-3-one and 2-hydroxy-4-N-octoxybenzophenone in a mass ratio of 1:1: 3.
As a further improvement of the invention, the plasticizer is a mixture of triaryl phosphate and chlorinated paraffin in a mass ratio of 3: 1; the lubricant is N, N' -ethylene bis stearamide; the filler is zinc borate.
As a further improvement of the invention, the preparation method of the cable material comprises the following steps:
the method comprises the following steps: preparing raw materials according to a set weight percentage, adding modified polyethylene, ethylene propylene diene monomer, a plasticizer, a lubricant and a filler into a mixer, and stirring and mixing; wherein the temperature of the mixer is set to be 50-60 ℃, the stirring time is 15-20 minutes, and the stirring speed is 400 rad/min;
step two: adding the flame retardant, the stabilizer and the anti-aging agent into a mixer, and stirring, wherein the temperature of the mixer is set to be 70-80 ℃, the stirring time is 30-40min, the stirring speed is 600rad/min, and the mixture is uniformly mixed;
step three: putting the mixed material into a double-screw extruder for extrusion molding to prepare a cable material; wherein the length-diameter ratio of the double-screw extruder is 40: 1; the temperatures of the sections are 150 ℃ in the first zone 140-.
The invention has the beneficial effects that: the modified polyethylene and the ethylene propylene diene monomer are taken as basic raw materials, and auxiliary agents such as a flame retardant, a stabilizer, an anti-aging agent and the like are added for reaction to obtain the modified polyethylene ethylene propylene diene monomer; the ethylene propylene diene monomer is a copolymer of ethylene, propylene and a small amount of non-conjugated diene, and has better heat resistance and weather resistance; the polyethylene is a thermoplastic material prepared by polymerizing ethylene and has better processability; as one of the creativity of the invention, in order to further improve the mechanical property of the polyethylene and simultaneously ensure that the polyethylene and other additives, particularly flame retardants have better compatibility, the invention carries out modification treatment on the polyethylene, takes the polyethylene as a raw material, takes tert-butyl peroxymaleate as an initiator, takes sodium dodecyl benzene sulfonate as a catalyst, and simultaneously adds a modifier, styrene and dimethylamino propyl methacryloyl to participate in reaction together, wherein the modifier selects a mixture of vinyltrimethoxysilane, 2, 3-bis (2,4, 5-trimethyl-3-thiophene) maleic anhydride and (3,3, 3-trifluoropropyl) trimethoxysilane, and under the combined action of the three substances, the polyethylene can be subjected to silane crosslinking treatment, and the tensile strength and the elongation at break of the modified polyethylene can be further improved by improving the crosslinking degree, the compatibility between the modified polyethylene and additives such as a flame retardant is improved, so that the mechanical property of the product is not influenced after the flame retardant is added into the system; and the heat resistance of the product can be further improved.
The invention also has the creativity that a flame retardant is added into the system, the flame retardant is a mixture of 6- (difluoromethoxy) -2- (trimethylsilyl) benzo [4,5] imidazo [2,1-b ] thiazole, 10- (2, 5-dihydroxyphenyl) -10-hydrogen-9-oxa-10-phosphaphenanthrene-10-oxide and triphenyl antimony oxide, wherein 6- (difluoromethoxy) -2- (trimethylsilyl) benzo [4,5] imidazo [2,1-b ] thiazole is prepared by taking trimethylacetylene silicon and difluoromethoxy-2-mercapto-1H-benzimidazole as raw materials, and contains active groups such as fluoro, phenyl, silicon, carbon-carbon double bonds and the like, on one hand, the modified polyethylene has higher compatibility with the modified polyethylene; on the other hand, the flame retardant property of the product can be improved; and the 10- (2, 5-dihydroxyphenyl) -10-hydrogen-9-oxa-10-phosphaphenanthrene-10-oxide and the triphenylantimony oxide can generate a synergistic effect with the 6- (difluoromethoxy) -2- (trimethylsilyl) benzo [4,5] imidazo [2,1-b ] thiazole, so that the flame retardant property of the product is further improved, and the final product belongs to a flame retardant material.
In addition, the invention selects a mixture of bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate, 1, 2-epoxy-4-vinyl cyclohexane and tributyl ethylene tin on the stabilizer; the anti-aging agent is selected from a mixture of (R) -N-epoxypropylphthalimide, 1-benzhydrylazetidin-3-one and 2-hydroxy-4-N-octoxybenzophenone; under the combined action of the anti-aging agent and the stabilizer, the cable material disclosed by the invention has higher thermal stability and stronger ultraviolet resistance, and still has higher mechanical properties after thermal aging and sunlight aging treatment.
The finally prepared cable material has high tensile strength and elongation at break, high flame retardant property, high tensile strength and elongation at break even after thermal aging and sunlight aging treatment, and wide application range.
Detailed Description
Example 1
The preparation method of 6- (difluoromethoxy) -2- (trimethylsilyl) benzo [4,5] imidazo [2,1-b ] thiazole comprises the following steps:
putting trimethyl acetylene silicon (0.1mol), 5-difluoromethoxy-2-mercapto-1H-benzimidazole (0.13mol), copper fluoride (0.025mol), 2, 9-diisopropyl-1, 10-phenanthroline (0.03mol), iodine simple substance (0.1mol) and cesium carbonate (0.2mol) into a reaction vessel filled with 200ml of toluene, and stirring and mixing; after being mixed evenly, the mixture reacts for 20 hours at the temperature of 70 ℃ to prepare 6- (difluoromethoxy) -2- (trimethylsilyl) benzo [4,5] imidazo [2,1-b ] thiazole;
the reaction formula is as follows:
Figure BDA0002340900050000071
characterization data:1H NMR(CDCl3,500MHz,ppm):δ7.54-7.32(m,2H),7.34-7.31(m,1H),7.10-6.89(m,2H),-0.31(s,9H).13C NMR(CDCl3,125MHz,ppm):δ167.0,155.9,143.1,141.2,135.8,120.3,119.7,116.6,111.3,100.6,2.5.
the structural formula of 6- (difluoromethoxy) -2- (trimethylsilyl) benzo [4,5] imidazo [2,1-b ] thiazole is shown in the specification
Figure BDA0002340900050000072
Example 2
The modified polyethylene comprises the following substances in parts by weight:
60 parts of polyethylene;
2 parts of tert-butyl peroxymaleate;
3 parts of sodium dodecyl benzene sulfonate;
2 parts of dimethylamino propyl methacryl;
2 parts of styrene;
7 parts of a modifier;
the modifier is a mixture of vinyl trimethoxy silane, 2, 3-bis (2,4, 5-trimethyl-3-thiophene) maleic anhydride and (3,3, 3-trifluoropropyl) trimethoxy silane, and the mass ratio of the modifier to the (3,3, 3-trifluoropropyl) trimethoxy silane is 1:1: 1.
The preparation method of the modified polyethylene comprises the following steps:
the method comprises the following steps: weighing the required materials according to the set weight parts, adding polyethylene, tert-butyl peroxymaleate, sodium dodecyl benzene sulfonate, dimethylaminopropyl methacrylyl and styrene into a reaction vessel filled with acetone, stirring and mixing, uniformly mixing, and then carrying out reaction at the temperature of 70 ℃ for 35min under the protection of nitrogen;
step two: then adding the modifier into a reaction vessel for continuous reaction, and reacting for 2.5h at the temperature of 90 ℃; filtering, purifying and drying after the reaction is finished to prepare the modified polyethylene.
Example 3
A cable material comprises the following substances in parts by weight:
75 parts of modified polyethylene;
25 minutes of ethylene propylene diene monomer;
12 parts of a flame retardant;
7 parts of a plasticizer;
3 parts of a stabilizer;
3 parts of an anti-aging agent;
1 part of a lubricant;
4 parts of a filler.
Wherein a modified polyethylene was prepared from example 2;
the flame retardant is a mixture of 6- (difluoromethoxy) -2- (trimethylsilyl) benzo [4,5] imidazo [2,1-b ] thiazole, 10- (2, 5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide and triphenyl antimony oxide, and the mass ratio of the flame retardant to the triphenyl antimony oxide is 2:3: 1; wherein 6- (difluoromethoxy) -2- (trimethylsilyl) benzo [4,5] imidazo [2,1-b ] thiazole was prepared from example 1;
the stabilizer is a mixture of bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate, 1, 2-epoxy-4-vinylcyclohexane and tributyl ethylene tin, and the mass ratio of the stabilizer to the tributylethylene tin is 2:1: 1.
The anti-aging agent is a mixture of (R) -N-epoxypropylphthalimide, 1-benzhydrylazetidine-3-ketone and 2-hydroxy-4-N-octoxybenzophenone in a mass ratio of 1:1: 3.
The plasticizer is a mixture of triaryl phosphate and chlorinated paraffin, and the mass ratio of the triaryl phosphate to the chlorinated paraffin is 3: 1;
the lubricant is N, N' -ethylene bis stearamide;
the filler is zinc borate.
The preparation method of the cable material comprises the following steps:
the method comprises the following steps: preparing raw materials according to a set weight percentage, adding modified polyethylene, ethylene propylene diene monomer, a plasticizer, a lubricant and a filler into a mixer, and stirring and mixing; wherein the temperature of the mixer is set to 55 ℃, the stirring time is 18 minutes, and the stirring speed is 400 rad/min;
step two: adding the flame retardant, the stabilizer and the anti-aging agent into a mixer, and stirring, wherein the temperature of the mixer is set to be 75 ℃, the stirring time is 35min, the stirring speed is 600rad/min, and the mixture is uniformly mixed;
step three: putting the mixed material into a double-screw extruder for extrusion molding to prepare a cable material; wherein the length-diameter ratio of the double-screw extruder is 40: 1; the temperatures of the sections are 150 ℃ in the first zone 140-.
Example 4
A cable material comprises the following substances in parts by weight:
80 parts of modified polyethylene;
20 minutes of ethylene propylene diene monomer;
11 parts of a flame retardant;
6 parts of a plasticizer;
3 parts of a stabilizer;
3 parts of an anti-aging agent;
2 parts of a lubricant;
3 parts of a filler.
Wherein a modified polyethylene was prepared from example 2;
the flame retardant is a mixture of 6- (difluoromethoxy) -2- (trimethylsilyl) benzo [4,5] imidazo [2,1-b ] thiazole, 10- (2, 5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide and triphenyl antimony oxide, and the mass ratio of the flame retardant to the triphenyl antimony oxide is 2:3: 1; wherein 6- (difluoromethoxy) -2- (trimethylsilyl) benzo [4,5] imidazo [2,1-b ] thiazole was prepared from example 1;
the stabilizer is a mixture of bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate, 1, 2-epoxy-4-vinylcyclohexane and tributyl ethylene tin, and the mass ratio of the stabilizer to the tributylethylene tin is 2:1: 1.
The anti-aging agent is a mixture of (R) -N-epoxypropylphthalimide, 1-benzhydrylazetidine-3-ketone and 2-hydroxy-4-N-octoxybenzophenone in a mass ratio of 1:1: 3.
The plasticizer is a mixture of triaryl phosphate and chlorinated paraffin, and the mass ratio of the triaryl phosphate to the chlorinated paraffin is 3: 1;
the lubricant is N, N' -ethylene bis stearamide;
the filler is zinc borate.
The preparation method of the cable material comprises the following steps:
the method comprises the following steps: preparing raw materials according to a set weight percentage, adding modified polyethylene, ethylene propylene diene monomer, a plasticizer, a lubricant and a filler into a mixer, and stirring and mixing; wherein the temperature of the mixer is set to 55 ℃, the stirring time is 18 minutes, and the stirring speed is 400 rad/min;
step two: adding the flame retardant, the stabilizer and the anti-aging agent into a mixer, and stirring, wherein the temperature of the mixer is set to be 75 ℃, the stirring time is 35min, the stirring speed is 600rad/min, and the mixture is uniformly mixed;
step three: putting the mixed material into a double-screw extruder for extrusion molding to prepare a cable material; wherein the length-diameter ratio of the double-screw extruder is 40: 1; the temperatures of the sections are 150 ℃ in the first zone 140-.
Example 5
A cable material comprises the following substances in parts by weight:
70 parts of modified polyethylene;
30 minutes of ethylene propylene diene monomer;
13 parts of a flame retardant;
8 parts of a plasticizer;
3 parts of a stabilizer;
3 parts of an anti-aging agent;
1 part of a lubricant;
and 5 parts of a filler.
Wherein a modified polyethylene was prepared from example 2;
the flame retardant is a mixture of 6- (difluoromethoxy) -2- (trimethylsilyl) benzo [4,5] imidazo [2,1-b ] thiazole, 10- (2, 5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide and triphenyl antimony oxide, and the mass ratio of the flame retardant to the triphenyl antimony oxide is 2:3: 1; wherein 6- (difluoromethoxy) -2- (trimethylsilyl) benzo [4,5] imidazo [2,1-b ] thiazole was prepared from example 1;
the stabilizer is a mixture of bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate, 1, 2-epoxy-4-vinylcyclohexane and tributyl ethylene tin, and the mass ratio of the stabilizer to the tributylethylene tin is 2:1: 1.
The anti-aging agent is a mixture of (R) -N-epoxypropylphthalimide, 1-benzhydrylazetidine-3-ketone and 2-hydroxy-4-N-octoxybenzophenone in a mass ratio of 1:1: 3.
The plasticizer is a mixture of triaryl phosphate and chlorinated paraffin, and the mass ratio of the triaryl phosphate to the chlorinated paraffin is 3: 1;
the lubricant is N, N' -ethylene bis stearamide;
the filler is zinc borate.
The preparation method of the cable material comprises the following steps:
the method comprises the following steps: preparing raw materials according to a set weight percentage, adding modified polyethylene, ethylene propylene diene monomer, a plasticizer, a lubricant and a filler into a mixer, and stirring and mixing; wherein the temperature of the mixer is set to 55 ℃, the stirring time is 18 minutes, and the stirring speed is 400 rad/min;
step two: adding the flame retardant, the stabilizer and the anti-aging agent into a mixer, and stirring, wherein the temperature of the mixer is set to be 75 ℃, the stirring time is 35min, the stirring speed is 600rad/min, and the mixture is uniformly mixed;
step three: putting the mixed material into a double-screw extruder for extrusion molding to prepare a cable material; wherein the length-diameter ratio of the double-screw extruder is 40: 1; the temperatures of the sections are 150 ℃ in the first zone 140-.
Comparative example 1
A cable material comprises the following substances in parts by weight:
75 parts of polyethylene;
25 minutes of ethylene propylene diene monomer;
12 parts of a flame retardant;
7 parts of a plasticizer;
3 parts of a stabilizer;
3 parts of an anti-aging agent;
1 part of a lubricant;
4 parts of a filler.
The flame retardant is a mixture of 6- (difluoromethoxy) -2- (trimethylsilyl) benzo [4,5] imidazo [2,1-b ] thiazole, 10- (2, 5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide and triphenyl antimony oxide, and the mass ratio of the flame retardant to the triphenyl antimony oxide is 2:3: 1; wherein 6- (difluoromethoxy) -2- (trimethylsilyl) benzo [4,5] imidazo [2,1-b ] thiazole was prepared from example 1;
the stabilizer is a mixture of bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate, 1, 2-epoxy-4-vinylcyclohexane and tributyl ethylene tin, and the mass ratio of the stabilizer to the tributylethylene tin is 2:1: 1.
The anti-aging agent is a mixture of (R) -N-epoxypropylphthalimide, 1-benzhydrylazetidine-3-ketone and 2-hydroxy-4-N-octoxybenzophenone in a mass ratio of 1:1: 3.
The plasticizer is a mixture of triaryl phosphate and chlorinated paraffin, and the mass ratio of the triaryl phosphate to the chlorinated paraffin is 3: 1;
the lubricant is N, N' -ethylene bis stearamide;
the filler is zinc borate.
The preparation method of the cable material comprises the following steps:
the method comprises the following steps: preparing raw materials according to a set weight percentage, adding polyethylene, ethylene propylene diene monomer, a plasticizer, a lubricant and a filler into a mixer, and stirring and mixing; wherein the temperature of the mixer is set to 55 ℃, the stirring is carried out for 18 minutes, and the stirring speed is 400 rad/min;
step two: adding the flame retardant, the stabilizer and the anti-aging agent into a mixer, and stirring, wherein the temperature of the mixer is set to be 75 ℃, the stirring is carried out for 35min, the stirring speed is 600rad/min, and the mixture is uniformly mixed;
step three: putting the mixed material into a double-screw extruder for extrusion molding to prepare a cable material; wherein the length-diameter ratio of the double-screw extruder is 40: 1; the temperatures of the sections are 150 ℃ in the first zone 140-.
Comparative example 2
A cable material comprises the following substances in parts by weight:
75 parts of modified polyethylene;
25 minutes of ethylene propylene diene monomer;
12 parts of a flame retardant;
7 parts of a plasticizer;
3 parts of a stabilizer;
3 parts of an anti-aging agent;
1 part of a lubricant;
4 parts of a filler.
Wherein a modified polyethylene was prepared from example 2;
the flame retardant is a mixture of 10- (2, 5-dihydroxyphenyl) -10-hydrogen-9-oxa-10-phosphaphenanthrene-10-oxide and triphenyl antimony oxide, and the mass ratio of the flame retardant to the triphenyl antimony oxide is 3: 1;
the stabilizer is a mixture of bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate, 1, 2-epoxy-4-vinylcyclohexane and tributyl ethylene tin, and the mass ratio of the stabilizer to the tributylethylene tin is 2:1: 1.
The anti-aging agent is a mixture of (R) -N-epoxypropylphthalimide, 1-benzhydrylazetidine-3-ketone and 2-hydroxy-4-N-octoxybenzophenone in a mass ratio of 1:1: 3.
The plasticizer is a mixture of triaryl phosphate and chlorinated paraffin, and the mass ratio of the triaryl phosphate to the chlorinated paraffin is 3: 1;
the lubricant is N, N' -ethylene bis stearamide;
the filler is zinc borate.
The preparation method of the cable material comprises the following steps:
the method comprises the following steps: preparing raw materials according to a set weight percentage, adding modified polyethylene, ethylene propylene diene monomer, a plasticizer, a lubricant and a filler into a mixer, and stirring and mixing; wherein the temperature of the mixer is set to 55 ℃, the stirring is carried out for 18 minutes, and the stirring speed is 400 rad/min;
step two: adding the flame retardant, the stabilizer and the anti-aging agent into a mixer, and stirring, wherein the temperature of the mixer is set to be 75 ℃, the stirring is carried out for 35min, the stirring speed is 600rad/min, and the mixture is uniformly mixed;
step three: putting the mixed material into a double-screw extruder for extrusion molding to prepare a cable material; wherein the length-diameter ratio of the double-screw extruder is 40: 1; the temperatures of the sections are 150 ℃ in the first zone 140-.
Performance testing
The tensile strength and elongation at break of the test sample are determined according to GB/T1040-2006 "determination of tensile Properties of plastics"; an HC-2 combustion oxygen index tester is adopted to measure the oxygen index of the sample according to GB/T2406 + 1993 'plastic combustion performance test method oxygen index method';
adopting an LHX-II high-temperature aging test box to perform an aging performance test on the cable according to GB/T2951.12-2008; an ultraviolet light aging resistance test is carried out by adopting a U.S. Q-Lab Q-SUN Xe-3 xenon lamp weather resistance test box according to ANSI/UL1581-2006, and a long-term photo-thermal aging environment is simulated.
The original tensile strength and elongation at break of the test specimen;
test specimen Tensile strength/MPa Elongation at break/%
Example 3 19.7 780
Example 4 18.3 710
Example 5 19.2 750
Comparative example 1 11.2 330
Comparative example 2 15.6 560
As can be seen from the above table, the cable material prepared by the present invention has a large tensile strength and a large elongation at break.
Tensile strength and elongation at break of the sample after thermal aging (150 ℃/168 h);
test specimen Tensile strength/MPa Elongation at break/%
Example 3 19.5 770
Example 4 18.1 705
Example 5 19.0 740
Comparative example 1 10.9 320
Comparative example 2 15.2 530
As can be seen from the above table, the cable material prepared by the invention still has higher tensile strength and elongation at break after being subjected to thermal aging treatment.
Tensile strength and elongation at break of the test sample after sunlight aging (720 h);
test specimen Tensile strength/MPa Elongation at break/%
Example 3 19.3 760
Example 4 18.0 695
Example 5 18.8 730
Comparative example 1 10.7 310
Comparative example 2 15.0 510
As can be seen from the above table, the cable material prepared by the invention still has large tensile strength and elongation at break after being subjected to sunlight aging treatment.
Figure BDA0002340900050000151
Figure BDA0002340900050000161
The high oxygen index indicates that the material is not easy to burn, the low oxygen index indicates that the material is easy to burn, the oxygen index is generally considered to be less than 22 and belongs to a combustible material, the oxygen index is between 22 and 27, and the oxygen index is more than 27 and belongs to a non-combustible material. As shown in the table, the cable material prepared by the invention belongs to a flame-retardant material, and the oxygen index of the cable material is still greater than 27 after the cable material is subjected to sunlight aging treatment, so that the cable material prepared by the invention has high flame retardant property and high safety.
The cable material is prepared by taking modified polyethylene and ethylene propylene diene monomer as basic raw materials and adding a flame retardant, a stabilizer, an anti-aging agent and other auxiliary agents for reaction; the ethylene propylene diene monomer is a copolymer of ethylene, propylene and a small amount of non-conjugated diene, and has better heat resistance and weather resistance; the polyethylene is a thermoplastic material prepared by polymerizing ethylene and has better processability; as one of the creativity of the invention, in order to further improve the mechanical property of the polyethylene and simultaneously ensure that the polyethylene and other additives, particularly flame retardants have better compatibility, the invention carries out modification treatment on the polyethylene, takes the polyethylene as a raw material, takes tert-butyl peroxymaleate as an initiator, takes sodium dodecyl benzene sulfonate as a catalyst, and simultaneously adds a modifier, styrene and dimethylamino propyl methacryloyl to participate in reaction together, wherein the modifier selects a mixture of vinyltrimethoxysilane, 2, 3-bis (2,4, 5-trimethyl-3-thiophene) maleic anhydride and (3,3, 3-trifluoropropyl) trimethoxysilane, and under the combined action of the three substances, the polyethylene can be subjected to silane crosslinking treatment, and the tensile strength and the elongation at break of the modified polyethylene can be further improved by improving the crosslinking degree, the compatibility between the modified polyethylene and additives such as a flame retardant is improved, so that the mechanical property of the product is not influenced after the flame retardant is added into the system; and the heat resistance of the product can be further improved.
The invention also has the creativity that a flame retardant is added into the system, the flame retardant is a mixture of 6- (difluoromethoxy) -2- (trimethylsilyl) benzo [4,5] imidazo [2,1-b ] thiazole, 10- (2, 5-dihydroxyphenyl) -10-hydrogen-9-oxa-10-phosphaphenanthrene-10-oxide and triphenyl antimony oxide, wherein 6- (difluoromethoxy) -2- (trimethylsilyl) benzo [4,5] imidazo [2,1-b ] thiazole is prepared by taking trimethylacetylene silicon and difluoromethoxy-2-mercapto-1H-benzimidazole as raw materials, and contains active groups such as fluoro, phenyl, silicon, carbon-carbon double bonds and the like, on one hand, the modified polyethylene has higher compatibility with the modified polyethylene; on the other hand, the flame retardant property of the product can be improved; and the 10- (2, 5-dihydroxyphenyl) -10-hydrogen-9-oxa-10-phosphaphenanthrene-10-oxide and the triphenylantimony oxide can generate a synergistic effect with the 6- (difluoromethoxy) -2- (trimethylsilyl) benzo [4,5] imidazo [2,1-b ] thiazole, so that the flame retardant property of the product is further improved, and the final product belongs to a flame retardant material.
In addition, the invention selects a mixture of bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate, 1, 2-epoxy-4-vinyl cyclohexane and tributyl ethylene tin on the stabilizer; the anti-aging agent is selected from a mixture of (R) -N-epoxypropylphthalimide, 1-benzhydrylazetidin-3-one and 2-hydroxy-4-N-octoxybenzophenone; under the combined action of the anti-aging agent and the stabilizer, the cable material disclosed by the invention has higher thermal stability and stronger ultraviolet resistance, and still has higher mechanical properties after thermal aging and sunlight aging treatment.
The finally prepared cable material has high tensile strength and elongation at break, high flame retardant property, high tensile strength and elongation at break even after thermal aging and sunlight aging treatment, and wide application range.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may occur to those skilled in the art without departing from the principle of the invention, and are considered to be within the scope of the invention.

Claims (10)

1. A cable material is characterized in that: the composition comprises the following substances in parts by weight:
70-80 parts of modified polyethylene;
20-30 minutes of ethylene propylene diene monomer;
10-15 parts of a flame retardant;
5-10 parts of a plasticizer;
2-4 parts of a stabilizer;
2-4 parts of an anti-aging agent;
1-2 parts of a lubricant;
3-5 parts of a filler.
2. The cable material of claim 1, wherein: the modified polyethylene comprises the following substances in parts by weight:
60 parts of polyethylene;
2 parts of tert-butyl peroxymaleate;
3 parts of sodium dodecyl benzene sulfonate;
2 parts of dimethylamino propyl methacryl;
2 parts of styrene;
7 parts of a modifier;
the modifier is a mixture of vinyl trimethoxy silane, 2, 3-bis (2,4, 5-trimethyl-3-thiophene) maleic anhydride and (3,3, 3-trifluoropropyl) trimethoxy silane, and the mass ratio of the modifier to the (3,3, 3-trifluoropropyl) trimethoxy silane is 1:1: 1.
3. The cable material of claim 2, wherein: the preparation method of the modified polyethylene comprises the following steps:
the method comprises the following steps: weighing the required materials according to the set weight parts, adding polyethylene, tert-butyl peroxymaleate, sodium dodecyl benzene sulfonate, dimethylaminopropyl methacrylyl and styrene into a reaction vessel filled with acetone, stirring and mixing, uniformly mixing, and reacting at the temperature of 60-80 ℃ for 30-40min under the protection of nitrogen;
step two: adding the modifier into a reaction vessel for continuous reaction, and reacting for 2-3h at the temperature of 80-100 ℃; filtering, purifying and drying after the reaction is finished to prepare the modified polyethylene.
4. A cable material according to claim 3, wherein: the flame retardant is a mixture of 6- (difluoromethoxy) -2- (trimethylsilyl) benzo [4,5] imidazo [2,1-b ] thiazole, 10- (2, 5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide and triphenyl antimony oxide, and the mass ratio of the flame retardant to the triphenyl antimony oxide is 2:3: 1;
wherein the structural formula of the 6- (difluoromethoxy) -2- (trimethylsilyl) benzo [4,5] imidazo [2,1-b ] thiazole is shown in the specification
Figure FDA0002340900040000021
The structural formula of the 10- (2, 5-dihydroxyphenyl) -10-hydrogen-9-oxa-10-phosphaphenanthrene-10-oxide is shown in the specification
Figure FDA0002340900040000022
The structural formula of the triphenyl antimony oxide is shown as
Figure FDA0002340900040000023
5. The cable material of claim 4, wherein: the preparation method of the 6- (difluoromethoxy) -2- (trimethylsilyl) benzo [4,5] imidazo [2,1-b ] thiazole comprises the following steps: putting trimethyl acetylene silicon, 5-difluoromethoxy-2-mercapto-1H-benzimidazole, a copper catalyst, a ligand, an oxidant and an alkaline substance into a reaction vessel filled with a solvent, and stirring and mixing; after being mixed evenly, the mixture reacts for 18 to 22 hours at the temperature of 60 to 80 ℃ to prepare 6- (difluoromethoxy) -2- (trimethylsilyl) benzo [4,5] imidazo [2,1-b ] thiazole;
the reaction formula is as follows:
Figure FDA0002340900040000031
6. the cable material of claim 5, wherein: the copper catalyst is copper fluoride;
the ligand is 2, 9-diisopropyl-1, 10-phenanthroline;
the oxidant is iodine simple substance;
the alkaline substance is cesium carbonate;
the solvent is toluene.
7. The cable material of claim 6, wherein: the stabilizer is a mixture of bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate, 1, 2-epoxy-4-vinylcyclohexane and tributyl ethylene tin, and the mass ratio of the stabilizer to the tributylethylene tin is 2:1: 1.
8. The cable material of claim 7, wherein: the anti-aging agent is a mixture of (R) -N-epoxypropylphthalimide, 1-benzhydrylazetidine-3-ketone and 2-hydroxy-4-N-octoxybenzophenone in a mass ratio of 1:1: 3.
9. The cable material of claim 8, wherein: the plasticizer is a mixture of triaryl phosphate and chlorinated paraffin, and the mass ratio of the triaryl phosphate to the chlorinated paraffin is 3: 1;
the lubricant is N, N' -ethylene bis stearamide;
the filler is zinc borate.
10. The cable material of claim 9, wherein: the preparation method of the cable material comprises the following steps:
the method comprises the following steps: preparing raw materials according to a set weight percentage, adding modified polyethylene, ethylene propylene diene monomer, a plasticizer, a lubricant and a filler into a mixer, and stirring and mixing; wherein the temperature of the mixer is set to be 50-60 ℃, the stirring time is 15-20 minutes, and the stirring speed is 400 rad/min;
step two: adding the flame retardant, the stabilizer and the anti-aging agent into a mixer, and continuously stirring and mixing, wherein the temperature of the mixer is set to be 70-80 ℃, the stirring time is 30-40min, and the stirring speed is 600rad/min, so as to prepare a mixed material;
step three: putting the mixed material into a double-screw extruder for extrusion molding to prepare a cable material; wherein the length-diameter ratio of the double-screw extruder is 40: 1; the temperatures of the sections are 150 ℃ in the first zone 140-.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113061217A (en) * 2021-05-13 2021-07-02 蒋春梅 Preparation method of novel flame retardant for polylactic acid
CN114516985A (en) * 2022-02-28 2022-05-20 成都金发科技新材料有限公司 Insulating coating material and application thereof

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CN106750799A (en) * 2016-12-20 2017-05-31 安徽华天电缆有限公司 A kind of tear-resistant PE cable material of good toughness
CN107641236A (en) * 2017-09-25 2018-01-30 常州市沃兰特电子有限公司 A kind of preparation method of flame-proof heat-resistant type poly-ethylene cable material

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CN106750799A (en) * 2016-12-20 2017-05-31 安徽华天电缆有限公司 A kind of tear-resistant PE cable material of good toughness
CN107641236A (en) * 2017-09-25 2018-01-30 常州市沃兰特电子有限公司 A kind of preparation method of flame-proof heat-resistant type poly-ethylene cable material

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113061217A (en) * 2021-05-13 2021-07-02 蒋春梅 Preparation method of novel flame retardant for polylactic acid
CN114516985A (en) * 2022-02-28 2022-05-20 成都金发科技新材料有限公司 Insulating coating material and application thereof

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