CN104761802A - Heat-resistant weather-resistant flame-retarding rubber insulating cable material - Google Patents

Heat-resistant weather-resistant flame-retarding rubber insulating cable material Download PDF

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Publication number
CN104761802A
CN104761802A CN201510120139.4A CN201510120139A CN104761802A CN 104761802 A CN104761802 A CN 104761802A CN 201510120139 A CN201510120139 A CN 201510120139A CN 104761802 A CN104761802 A CN 104761802A
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parts
resistant
cable material
heat
ethylene
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管新元
张新
曹卫建
陈文博
张仲韬
邬振林
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Jiangsu Hengtong Power Cable Co Ltd
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Jiangsu Hengtong Power Cable Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • 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
    • 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
    • H01B3/443—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 vinylhalogenides or other halogenoethylenic compounds
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Organic Insulating Materials (AREA)

Abstract

The invention discloses a heat-resistant weather-resistant flame-retarding rubber insulating cable material which is composed of following components, by weight: 8-14 parts of chlorinated polyethylene (CPE), 15-21 parts of ethylene-octylene copolymer elastomer, 3-6 parts of fumed silica, 15-19 parts of aluminum hydroxide, 13-18 parts of calcined argil, 5-8 parts of 800# paraffin-based rubber oil, 0.5-1 part of activated magnesium oxide, 4-7 parts of ultrafine talcum powder, 1-2 parts of zinc oxide, 0.3-0.6 parts of an environmental-protective stabilizing agent, 1-2 parts of microcrystalline wax, 0.5-1 part of titanium dioxide, 0.5-0.8 parts of 4,4'-bis([alpha],[alpha]-dimethylbenzyl)diphenylamine, 1-2 parts of dicumyl peroxide, and 1-1.5 parts of triallyl cyanurate. In the ethylene-octylene copolymer elastomer, the mass percentage of octylene monomer is 20-30%. The cable material is beneficial to uniformity of addition of organic powders, is wide in technical range, can maintain a high elongation at break even at a continuous vulcanizing temperature of 190-210 DEG C. With addition of same filling materials, the cable material requires less plasticizing agent and can improve heat-resistant and weather-resistant performances of rubber compound.

Description

Heat-resisting weathering resistance flame retardant rubber insulated cable material
Technical field
The present invention relates to flame retardant rubber insulated cable material, be specifically related to a kind of heat-resisting weathering resistance flame retardant rubber insulated cable material.
Background technology
What commonly use in rubber insulation is that Ethylene Propylene Terpolymer is as base-material, with vulcanizing agent DCP and vulcanization accelerator TAC, the shortcoming of rubber unvulcanizate is: elongation at break lower (elongation at break is generally 150% ~ 250%), in sulfidation, processing range is narrower, is easy to elongation at break defective during steam vulcanization.
Summary of the invention
The object of this invention is to provide a kind of heat-resisting weathering resistance flame retardant rubber insulated cable material, be conducive to inorganic powder dispersed, processing range is wide, and endless vulcanization temperature still keeps higher elongation at break between 190 DEG C ~ 210 DEG C, can greatly reduce costs simultaneously;
For achieving the above object, the technical solution used in the present invention is: a kind of heat-resisting weathering resistance flame retardant rubber insulated cable material, is characterized in that: be made up of the component of following weight part:
Chlorinatedpolyethylene (CPE) 12 ~ 14 parts,
18 ~ 20 parts, ethylene-octene copolymer elastomerics (POE)
Thermal silica 3 ~ 6 parts,
15 ~ 19 parts, aluminium hydroxide,
Calcinated argil 13 ~ 18 parts,
800# paraffinic base rubber oil 5 ~ 7 parts,
Activated magnesia 0.8 part,
Superfine talcum powder 5 ~ 7 parts,
1 ~ 1.5 part, zinc oxide,
Stabilizer 0.45 ~ 0.55 part,
Microcrystalline Wax 1.5 ~ 2 parts,
Titanium dioxide 0.7 ~ 0.9 part,
4,4 ' two (α, α dimethyl benzyl) pentanoic 0.5 ~ 0.6 part,
Dicumyl peroxide 1.5 parts,
Triallyl cyanurate 1.2 ~ 1.3 parts;
In described ethylene-octene copolymer elastomerics, the mass fraction of octene monomers is between 20% ~ 30%.
Further improvement project in above-mentioned fabricating technology scheme is as follows:
In such scheme, in described step 4, filter screen is three metafiltration nets, is respectively 40 orders, 80 orders and 40 orders.
Due to the utilization of technique scheme, the present invention compared with prior art has following advantages:
1. the present invention's heat-resisting weathering resistance flame retardant rubber insulated cable material, its adopt the mass fraction of octene monomers 20% ~ 30% 15 ~ 21 parts, ethylene-octene copolymer elastomerics (POE) and chlorinatedpolyethylene (CPE) 8 ~ 14 parts as base-material, due to mass fraction 20% ~ 30% the elastomeric Mooney of ethylene-octene copolymer be that 17 viscosity are lower, when temperature raises, sizing material deliquescing; Like this can moistening inorganic powder, be conducive to inorganic powder to be scattered in uniformly in base-material, improve consistency, and after with the addition of chlorinatedpolyethylene (CPE), because chlorinatedpolyethylene (CPE) Mooney is higher, overcome POE when mixing, put glue difficulty, avoid defect tri-roll press machine opened bar slice and easily break, improve physical and mechanical properties, under the prerequisite ensureing electrical property, processing performance is greatly improved; POE excellent electrical property, and chlorinated polyethylene compound can improve and use the electric property of rubber unvulcanizate; Secondly, 15 ~ 21 parts, the ethylene-octene copolymer elastomerics (POE) of mass fraction 20% ~ 30% and chlorinatedpolyethylene (CPE) 8 ~ 14 parts are as base-material, mooney viscosity is lower, adding identical packing material, softening agent required when reaching identical mooney viscosity is less, can improve heat-resisting, the weather resistance of rubber unvulcanizate like this.Finally, CPE as body material a part due in its molecular chain containing chlorine element, decomposes, generates non-flammable gases, inflammable gas and oxygen dilution is reached flame retardant effect.
2. the present invention's heat-resisting weathering resistance flame retardant rubber insulated cable material, its ethylene-octene copolymer elastomerics (POE) and chlorinatedpolyethylene (CPE) are all the not double bond containing saturated rubber of main chain, they have covulcanization characteristic, select DCP as vulcanizing agent, add co-curing agent triallyl cyanurate (TAC); When adopting DCP as vulcanization system, crosslinked and fracture occurs simultaneously, and for suppressing cleavage reaction, can add the common sulphur agent with functional group, co-curing agent can accelerate vulcanization rate greatly, improves cross-linking density, improves the heat resistance of cross-linked rubber.CPE itself does not have double bond, the point of crosslinking structure is not had yet, be cross-linked by superoxide completely, the radical that high temperature when sulfuration makes peroxide breakdown produce, capture the hydrogen on CPE long chain molecule and occur the radical of CPE, under the help of vulcanization aid TAC, the radical of two macromolecular chains being coupled together, form cross-linked structure, thus make the CPE vulcanization of rubber.In the process because the effect of polar molecule has the generation of HCl molecule, this HCl gas not only hampers colloid sulfuration, and easily makes CPE rubber produce similar sponge-type porosity but its physical and mechanical properties worsens.Adding of activated magnesia effectively overcomes this problem.So magnesium oxide is good acid-acceptor, vulcanization accelerator, CPE thermo-stabilizer.Zinc oxide can significantly improve vulcanization rate and the crosslinking degree of POE.
3. the present invention's heat-resisting weathering resistance flame retardant rubber insulated cable material, it is long-pending large that its thermal silica has particle diameter small specific surface, and the feature that surfactivity is high, has good strengthening action to rubber unvulcanizate, substantially increases the physical and mechanical properties of blend rubber; Aluminium hydroxide decomposes can absorb heat; be conducive to cooling; promote dehydrogenation reaction and protection carbon-coating; decompose the water of releasing and be not only a refrigerant, or a thinner, decompose under aluminium hydroxide high temperature and generate aluminium sesquioxide tectum; be covered in the surface of superpolymer; isolated heat, oxygen transmission, make the combustibility of material decline, and oxygen index increases.Aluminium hydroxide is added to the oxygen index that can improve rubber unvulcanizate in chlorinated polyethylene rubber; Calcinated argil is a kind of inorganic filler taking out crystal water more than 900 DEG C, its stable chemical performance, extruded product smooth in appearance, there is thermotolerance, the feature of resistance to acids and bases and good electrical property, and play strengthening action equally, and cost is lower, cost is made greatly to reduce like this.
Embodiment
The heat-resisting weathering resistance flame retardant rubber insulated cable material of embodiment 1. 1 kinds, material each component formula is: chlorinatedpolyethylene (CPE) 12 kilograms, 19 kilograms, ethylene-octene copolymer elastomerics (POE), 800# paraffinic base rubber oil 5 kilograms, activated magnesia 0.8 kilogram, 1.5 kilograms, zinc oxide, superfine talcum powder 5 kilograms, stabilizer 0.5 kilogram, Microcrystalline Wax 1.5 kilograms, titanium dioxide 0.8 kilogram, thermal silica 3 kilograms, calcinated argil 13 kilograms, 19 kilograms, aluminium hydroxide, 4, 4 ' two (α, α dimethyl benzyl) pentanoic 0.6 kilogram, dicumyl peroxide 1.5 kilograms, triallyl cyanurate 1.2 kilograms.
In above-mentioned ethylene-octene copolymer elastomerics, the mass fraction of octene monomers is 20% ~ 30%.
Preparation method: first by chlorinatedpolyethylene (CPE), ethylene-octene copolymer elastomerics (POE) percentage ratio mixing 4-5min in 90 ~ 110 DEG C of Banbury mixeies by weight, bi-material mixes; 800# paraffinic base rubber oil, activated magnesia, zinc oxide, stabilizer, Microcrystalline Wax, titanium dioxide, anti-aging agent 4,4 ' two (α, α dimethyl benzyl) pentanoic, mixing 2-3min; Then by calcinated argil, thermal silica, aluminium hydroxide, superfine talcum powder, mixing 3-5min; Banbury mixer discharge, by rubber unvulcanizate thin-pass 1 ~ 2 time on a mill until, put glue 2 ~ 3 times simultaneously, then rubber (the order number of three metafiltration nets is respectively: 40 orders, 80 orders, 40 orders) is filtered, after the rubber filtered is deposited 24 hours, sizing material is reentered into mixer mixing, add vulcanizing agent dicumyl peroxide, mixing about the 2 ~ 3min discharge of vulcanization aid triallyl cyanurate simultaneously, by rubber unvulcanizate thin-pass 1 ~ 2 time on a mill until, put glue 2 ~ 3 times simultaneously, tri-roll press machine is opened bar slice, rubber page cools through cooling roller, obtained finished product after powder case.
The high strength prepared of this example is high stretches rate flame retardant rubber insulated cable material, and performance detection data is as follows:
Aging condition: 135 ± 1 DEG C × 168 hours.
The heat-resisting weathering resistance flame retardant rubber insulated cable material of embodiment 2. 1 kinds, material each component formula is: chlorinatedpolyethylene (CPE) 12 kilograms, 19 kilograms, ethylene-octene copolymer elastomerics (POE), 800# paraffinic base rubber oil 7 kilograms, activated magnesia 0.8 kilogram, 1.5 kilograms, zinc oxide, superfine talcum powder 7 kilograms, stabilizer 0.5 kilogram, Microcrystalline Wax 1.5 kilograms, titanium dioxide 0.8 kilogram, thermal silica 3 kilograms, calcinated argil 17 kilograms, 19 kilograms, aluminium hydroxide, 4, 4 ' two (α, α dimethyl benzyl) pentanoic 0.6 kilogram, dicumyl peroxide 1.5 kilograms, triallyl cyanurate 1.2 kilograms.
In above-mentioned ethylene-octene copolymer elastomerics, the mass fraction of octene monomers is 22% ~ 24%.
Preparation method is in the same manner as in Example 1.
The high strength prepared of this example is high stretches rate flame retardant rubber insulated cable material, and performance detection data is as follows:
Aging condition: 135 ± 1 DEG C × 168 hours.
The heat-resisting weathering resistance flame retardant rubber insulated cable material of embodiment 3. 1 kinds, material each component formula is: chlorinatedpolyethylene (CPE) 14 kilograms, 18 kilograms, ethylene-octene copolymer elastomerics (POE), 800# paraffinic base rubber oil 5 kilograms, activated magnesia 0.8 kilogram, 1.0 kilograms, zinc oxide, superfine talcum powder 5 kilograms, stabilizer 0.5 kilogram, Microcrystalline Wax 2 kilograms, titanium dioxide 0.8 kilogram, thermal silica 5 kilograms, calcinated argil 17 kilograms, 19 kilograms, aluminium hydroxide, 4, 4 ' two (α, α dimethyl benzyl) pentanoic 0.6 kilogram, dicumyl peroxide 1.5 kilograms, triallyl cyanurate 1.2 kilograms.
In above-mentioned ethylene-octene copolymer elastomerics, the mass fraction of octene monomers is 25% ~ 26%.
The high strength prepared of this example is high stretches rate flame retardant rubber insulated cable material, and the detection data of performance are as follows:
Aging condition: 135 ± 1 DEG C × 168 hours.
To sum up, the present invention's heat-resisting weathering resistance flame retardant rubber insulated cable material, its adopt the mass fraction of octene monomers 20% ~ 30% 15 ~ 21 parts, ethylene-octene copolymer elastomerics (POE) and chlorinatedpolyethylene (CPE) 8 ~ 14 parts as base-material, due to mass fraction 20% ~ 30% the elastomeric Mooney of ethylene-octene copolymer be that 17 viscosity are lower, when temperature raises, rubber unvulcanizate becomes very soft; Being conducive to inorganic powder interpolation is mixed in its base-material uniformly, improve consistency, and after with the addition of chlorinatedpolyethylene (CPE), because chlorinatedpolyethylene (CPE) Mooney is higher, overcome rubber unvulcanizate when mixing, put glue difficulty, avoid defect tri-roll press machine opened bar slice and easily break, improve physical and mechanical properties, under the prerequisite ensureing electrical property, processing performance is greatly improved; Secondly, mass fraction 20% ~ 30% 15 ~ 21 parts, ethylene-octene copolymer elastomerics (POE) and chlorinatedpolyethylene (CPE) 8 ~ 14 parts as base-material, mooney viscosity is lower, adding identical packing material, softening agent required when reaching identical mooney viscosity is less, can improve the heat-resisting, weather-proof of rubber unvulcanizate like this.
Above-described embodiment, only for technical conceive of the present invention and feature are described, its object is to person skilled in the art can be understood content of the present invention and implement according to this, can not limit the scope of the invention with this.All equivalences done according to spirit of the present invention change or modify, and all should be encompassed within protection scope of the present invention.

Claims (1)

1. a heat-resisting weathering resistance flame retardant rubber insulated cable material, is characterized in that: be made up of the component of following weight part:
Chlorinatedpolyethylene (CPE) 12 ~ 14 parts,
18 ~ 20 parts, ethylene-octene copolymer elastomerics (POE)
Thermal silica 3 ~ 6 parts,
15 ~ 19 parts, aluminium hydroxide,
Calcinated argil 13 ~ 18 parts,
800# paraffinic base rubber oil 5 ~ 7 parts,
Activated magnesia 0.8 part,
Superfine talcum powder 5 ~ 7 parts,
1 ~ 1.5 part, zinc oxide,
Stabilizer 0.45 ~ 0.55 part,
Microcrystalline Wax 1.5 ~ 2 parts,
Titanium dioxide 0.7 ~ 0.9 part,
4,4 ' two (α, α dimethyl benzyl) pentanoic 0.5 ~ 0.6 part,
Dicumyl peroxide 1.5 parts,
Triallyl cyanurate 1.2 ~ 1.3 parts;
In described ethylene-octene copolymer elastomerics, the mass fraction of octene monomers is between 20% ~ 30%.
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CN105524324A (en) * 2016-01-23 2016-04-27 安徽瑞昊缆业有限公司 Formula of insulator of super flexible cable
CN111196885A (en) * 2020-03-23 2020-05-26 芜湖融汇化工有限公司 Ethylene-propylene-diene monomer insulating low-voltage rubber

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CN103756080B (en) * 2013-12-19 2016-01-06 安徽特力电缆有限公司 A kind of ageing-resistant flame-retardant modified polyolefin elastomer cable jacket material
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CN105733085B (en) * 2014-08-11 2020-06-02 江苏理工学院 Halogen-free flame-retardant POE material
CN104987583A (en) * 2015-07-17 2015-10-21 连云港德翔新材料有限公司 Ethylene-octene copolymer high performance composite material and preparation method thereof
CN107177114A (en) * 2017-05-09 2017-09-19 广西桂山特种橡胶制品有限公司 A kind of electro-insulating rubber product and its preparation technology
CN114773718A (en) * 2022-02-22 2022-07-22 徐州工业职业技术学院 High-strength high-elongation flame-retardant rubber insulated cable material and processing equipment and process thereof
CN114806030B (en) * 2022-04-18 2023-11-24 镇江中佳电器有限公司 Heat-resistant moisture-resistant insulating cable material and preparation process thereof

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CN105524324A (en) * 2016-01-23 2016-04-27 安徽瑞昊缆业有限公司 Formula of insulator of super flexible cable
CN111196885A (en) * 2020-03-23 2020-05-26 芜湖融汇化工有限公司 Ethylene-propylene-diene monomer insulating low-voltage rubber

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CN104829936A (en) 2015-08-12
CN103232630A (en) 2013-08-07
CN103232630B (en) 2015-08-19
CN104829936B (en) 2017-01-25

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