CN109438813A - Nuclear island inner cable halogen-free flameproof external insulation material, cable outer insulation and preparation method - Google Patents

Nuclear island inner cable halogen-free flameproof external insulation material, cable outer insulation and preparation method Download PDF

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Publication number
CN109438813A
CN109438813A CN201811305098.6A CN201811305098A CN109438813A CN 109438813 A CN109438813 A CN 109438813A CN 201811305098 A CN201811305098 A CN 201811305098A CN 109438813 A CN109438813 A CN 109438813A
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agent
nuclear island
inner cable
free flameproof
halogen
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Inventor
张立刚
王长春
张聪
朱峰
洪启付
郭大利
鲍蕾蕾
史佳麟
夏同方
胡敦胜
李吉豪
蒋海青
陆权
崔媛媛
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Qingdao Zhongke Hanlan High Molecular Material Co ltd
Changzhou Bayi Cable Co ltd
Shanghai Institute of Applied Physics of CAS
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Qingdao Zhongke Hanlan High Molecular Material Co ltd
Changzhou Bayi Cable Co ltd
Shanghai Institute of Applied Physics of CAS
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Application filed by Qingdao Zhongke Hanlan High Molecular Material Co ltd, Changzhou Bayi Cable Co ltd, Shanghai Institute of Applied Physics of CAS filed Critical Qingdao Zhongke Hanlan High Molecular Material Co ltd
Priority to CN201811305098.6A priority Critical patent/CN109438813A/en
Publication of CN109438813A publication Critical patent/CN109438813A/en
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    • C08J3/28—Treatment by wave energy or particle radiation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H01B13/06—Insulating conductors or cables
    • H01B13/14—Insulating conductors or cables by extrusion
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    • 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
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    • 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
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/02—Disposition of insulation
    • H01B7/0208—Cables with several layers of insulating material
    • H01B7/0216—Two layers
    • 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
    • H01B7/0275—Disposition of insulation comprising one or more extruded layers of insulation
    • H—ELECTRICITY
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    • 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
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    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
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Abstract

The invention discloses a kind of nuclear island inner cable halogen-free flameproof external insulation material, cable outer insulation and preparation methods.The nuclear island inner cable halogen-free flameproof external insulation material raw material includes: polymeric substrate, inorganic fire retardants, zinc borate, polyphosphazene flame retardant, phosphorus-nitrogen containing flame retardant, pin fumicants, anti-aging agent, composite antioxidant, anti-irradiation agent and processing aid.Preparation method is to be promoted to dual-band twin-screw extruder, air-cooled extruding pelletization after being kneaded polymeric substrate, inorganic fire retardants, zinc borate, polyphosphazene flame retardant, phosphorus-nitrogen containing flame retardant, anti-aging agent, pin fumicants, composite antioxidant, anti-irradiation agent.The Insulation Material has extra long life (90 DEG C >=70 years), high radiation resistance (gamma-rays, >=2400kGy) and good flame retardant property (insulation core wire is burnt by single vertical), and low cigarette, Halogen, low toxicity.

Description

Nuclear island inner cable halogen-free flameproof external insulation material, cable outer insulation and preparation method
Technical field
The invention belongs to nuclear island inner cable Insulation Material fields, and in particular to a kind of nuclear island inner cable halogen-free flameproof external insulation Material, cable outer insulation and preparation method.
Background technique
Nuclear power is a kind of safe and clean, economic energy.The heaps such as three generations's nuclear power such as AP1000, CAP1400, the imperial No.1 of China Long Service Life is 60 years at being promoted to 90 DEG C on the basis of type is Long Service Life 40 years at two 90 DEG C of generation nuclear power heap-type.Core Nuclear power 1 E-level cable used in power station (especially K1 cable in nuclear island) working environment is very harsh, in entire lifetime, Cable must be subjected to the multifactor intersection such as electric field, temperature, oxygen, nuclear radiation, steam moisture and chemicals under the conditions of nuclear environment In the comprehensive function of one.But when operating normally, humidity, chemical substance etc. influence very little to the aging of cable, and extreme item The influence of humidity, chemical substance under part can be tested by LOCA and immersion test is detected, to the various examinations of nuclear power cable It tests mainly to cable material accelerated aging test, nuclear power is studied by heat aging performance and radiation aging Performance Assessment Test It stands and is changed with the physical and chemical performance of cable material, study the environmental factors such as long-term electric field, heat, irradiation, oxygen to cable material The influence of material predicts the service life of cable to assess its safety in turn.
The sill of cable for nuclear power station insulating materials is usually polyethylene, crosslinked polyethylene, ethylene propylene diene rubber and second Alkene-octene copolymer etc., under long term heat ageing effect and a large amount of radiation exposure, insulating materials easily becomes fragile, mechanical performance Phenomena such as variation, the elongation at break of especially material declines to a great extent, influence materials'use.
1E grades of cables of used in nuclear power station (especially K1 cable in nuclear island) insulating layer must be fired by low smoke and zero halogen single vertical Burn test, while cable insulation intensity >=3760M Ω km, in order to meet the above binomial performance, at present used in nuclear power station 1E grade it is electric Cable (especially K1 cable in nuclear island) insulating layer uses double-layer structure, and internal layer uses and do not add fire retardant Halogen insulating materials (such as Low density polyethylene (LDPE) (LDPE), ultra-low density polyethylene (VLDPE), ethylene propylene diene rubber (EPDM) and ethylene-octene copolymer (POE)), outer layer uses low-smoke halide-free fireproof composite polyolefine material.A seed nucleus as disclosed in Chinese patent (CN102952316B) is used Cable halogen-free flame retardant insulation material, specific formula are as follows: low density polyethylene (LDPE) and ethylene propylene diene rubber: 100 parts；Inorganic fire retardants includes Magnesium hydroxide: 70-100 parts；Polyphosphazene flame retardant includes hexaphenoxycyclotriphosphazene: 10-20 parts；Composite antioxidant includes main anti- Oxygen agent, auxiliary antioxidant and ultraviolet absorbing agent: 4-8 parts；Anti-irradiation agent includes anti-irradiation agent A and B:5-15 parts of anti-irradiation agent: Processing aid includes crosslinking sensitizer and lubricant: 4-10 parts；Wherein anti-irradiation agent A is high phenyl siloxane rubber and/or penylene silicon Rubber；Anti-irradiation agent B is boron carbide and/or boron nitride.The Insulation Material has stable radiation-resistant property and electric property, good Flame retardant property, and low cigarette, Halogen, low toxicity.There are the Insulation Material 60 years service lifes of three generations's nuclear power and the γ of resistance to 1500kGy to penetrate Line.But there is still a need for further promoted for the material tensile strength, ageing-resistant and radiation-resistant property.
The nuclear power stations such as three generations's nuclear power such as AP1000, the imperial No.1 of China, it is higher than the requirement of two generations in terms of security performance, therefore, On the basis of two generation nuclear powers, harsher requirement is proposed to nuclear power generating equipment radiation aging and accident Irradiation Test, On the basis of gamma-ray irradiation test, the test of low dose rate static state β x ray irradiation x is increased, the energy of β radiation is 1.2MeV, It is that 20,000 lattice are auspicious (20kGy/h) per hour that condition, which is strictly set to dosage rate, and static shape is in when sample β x ray irradiation x tests State, AP1000 total absorbed dose are 2700kGy, and China's dragon No.1 total absorbed dose is 1800kGy, to investigate relevant device, instrument Or the low dose rate static state β x ray irradiation x damage of material (such as wire and cable), it is penetrated by the β ray that Xi Wo company, the U.S. carries out with γ It is 1.8:1 that line, which irradiates equivalent test result,.Three generations's nuclear power cable outer insulating material polymeric substrate uses LDPE and ternary at present EP rubbers is blended, and material tensile strength is lower, adds the mechanical performance that a large amount of fire retardants significantly reduce cable material, therefore It needs to carry out further to study to promote the comprehensive performance of cable insulation material.
Summary of the invention
Technical problem to be solved by the present invention lies in overcome existing insulating materials heat ageing and radioresistance that can expire All three generations's nuclear power cable insulating requirements of foot, the defects of halogen-free flameproof performance is not ideal enough, provide in nuclear island and are hindered with cable Halogen The preparation method and application for firing external insulation material, cable outer insulation make it have extra long life (90 DEG C, >=70 years), high resistance to spoke It is burnt according to performance (gamma-rays, >=2400kGy), insulating layer by single vertical, and low cigarette, Halogen, low toxicity.
One of technical solution of the present invention is to provide a kind of nuclear island inner cable halogen-free flameproof outer insulating material comprising with The raw material of lower parts by weight meter: 90-112 parts of polymeric substrate；60-80 parts of inorganic fire retardants；10-20 parts of zinc borate；Polyphosphazene resistance Agent 8-12 parts of combustion；10-20 parts of phosphorus-nitrogen containing flame retardant；Fumicants 1-3 parts of pin；1-3 parts of anti-aging agent；4-8 parts of composite antioxidant；Flouride-resistani acid phesphatase 3-8 parts of agent: 5-10 parts of processing aid；
Wherein, the polymeric substrate includes low density polyethylene (LDPE) (LDPE), ultra-low density polyethylene (VLDPE), three First EP rubbers (EPDM) and ethylene-octene copolymer (POE)；
The processing aid includes crosslinking sensitizer and lubricant；
The inorganic fire retardants includes magnesium hydroxide；
The polyphosphazene flame retardant includes hexaphenoxycyclotriphosphazene and the poly- polyphosphazene of phenoxy group；
The phosphorus-nitrogen containing flame retardant includes hypo-aluminum orthophosphate；
The composite antioxidant includes primary antioxidant, auxiliary antioxidant and ultraviolet absorbing agent；
Wherein, the primary antioxidant includes pentaerythritol ester and/or β-(3,5- di-tert-butyl -4- hydroxy phenyl) propionic acid Octadecyl ester；
The auxiliary antioxidant includes sulphur ester antioxidant；
The ultraviolet absorbing agent includes 2- (bis- tertiary amyl phenyl of 2'- hydroxyl -3', 5'-) benzotriazole, 2- (2'- hydroxyl Base -5'- spy octyl phenyl) in benzotriazole or 2- (bis- (a, a- dimethyl benzyl) phenyl of 2'- hydroxyl -3', 5'-) benzotriazole One or more.
The anti-irradiation agent includes anti-irradiation agent A and anti-irradiation agent B, wherein anti-irradiation agent A be high phenyl siloxane rubber and/ Or phenylene silicone rubber；Anti-irradiation agent B is boron carbide and/or boron nitride；
Wherein, the crosslinking sensitizer includes trimethylol-propane trimethacrylate and/or triallyl different three Polycyanate ester, the lubricant include one or more of polyethylene wax, zinc stearate or calcium stearate.
Wherein, the ingredient of above-mentioned substance and content are as previously described.
Preferably, the low density polyethylene (LDPE) (LDPE), ultra-low density polyethylene (VLDPE), ternary second in the present invention The mass ratio of third rubber (EPDM) and ethylene-octene copolymer (POE) is 50-60:20-30:10-15:10-15.
More preferably, the ultra-low density polyethylene (VLDPE) is the VLDPE-DFDB-6005NT (cable of DOW Chemical Expect grade)；
Preferably, the mass ratio of above-described hexaphenoxycyclotriphosphazene and the poly- polyphosphazene of phenoxy group is in the present invention 10-15:0-5。
In the present invention preferably, the sulphur ester antioxidant be dilauryl thiodipropionate (anti-oxidant DLTP) and/ Or the double octadecyl esters (antioxidant DSTP) of thio-2 acid.
In the present invention, preferably, the ultraviolet absorbing agent is 2- (bis- tertiary amyl phenyl of 2'- hydroxyl -3', 5'-) benzene And triazole (UV-328).
Preferably, the mass ratio of the additive amount of the primary antioxidant, auxiliary antioxidant and ultraviolet absorbing agent is 1:1- 3:0.1-0.5。
Preferably, the addition mass ratio of the anti-irradiation agent A and anti-irradiation agent B is 3-4:1-2 in the present invention.
Preferably, the high phenyl siloxane rubber phenyl content is 40%；
More preferably, the penylene base silicon rubber penylene content is 60%, phenyl content 30%；
Preferably, the mass ratio of the crosslinking sensitizer and lubricant is 1:1-2 in the present invention.
Preferably, the processing aid further includes environment-friendly type Masterbatch；The environment-friendly type Masterbatch, crosslinking sensitizer Mass ratio with lubricant is 1.5-4:1-2:1.5-4.
Preferably, the preparation method of the nuclear island inner cable halogen-free flameproof outer insulating material in the present invention, by polymer Substrate, zinc borate, polyphosphazene flame retardant, phosphorus-nitrogen containing flame retardant, anti-aging agent, pin fumicants, composite antioxidant, resists inorganic fire retardants Irradiation agent B and lubricant are put into mixer and are kneaded, and are kneaded 5 minutes after melting to 130 DEG C or so, crosslinking sensitizer is then added And anti-irradiation agent A, it is kneaded 5-10 minutes, is then lifted out to dual-band twin-screw extruder in 130-150 DEG C of temperature range, Air-cooled extruding pelletization in 120-160 DEG C of temperature range.
When in raw material contain environment-friendly type Masterbatch when, step include: by polymeric substrate, inorganic fire retardants, zinc borate, Polyphosphazene flame retardant, phosphorus-nitrogen containing flame retardant, anti-aging agent, pin fumicants, composite antioxidant, anti-irradiation agent B, lubricant and environment-friendly type color Master batch is put into mixer and is kneaded, and is kneaded 5 minutes after melting to 130 DEG C or so, crosslinking sensitizer and anti-irradiation agent is then added A is kneaded 5-10 minutes in 130-150 DEG C of temperature range, is then lifted out to dual-band twin-screw extruder, in 120-160 DEG C of temperature Spend air-cooled extruding pelletization in range.
The two of technical solution of the present invention are to provide a kind of nuclear island inner cable halogen-free flameproof external insulation layer material, this is outer absolutely The raw material of edge layer material includes above-described nuclear island inner cable halogen-free flameproof outer insulating material.
For the preparation method of the above nuclear island inner cable halogen-free flameproof external insulation layer material, by the nuclear island inner cable Halogen Fire-retardant outer insulating material melts at a temperature of two single screw extrusion machines are at 120-160 DEG C with nuclear island inner cable Halogen interior insulation material Double-layer coextrusion goes out, and is coated on copper conductor, crosslinking with radiation.The radiation source of the radiation is electron beam, the radiation Irradiation dose 150-200KGy.
The above specific preparation process can refer to: GB/T12706.1-2008.
On the basis of common knowledge of the art, above-mentioned each optimum condition, can any combination to get each preferable reality of the present invention Example.
Halogen-free flameproof outer insulating material has stable radiation-resistant property and electric property, good in nuclear island provided by the invention Good flame retardant property, and low cigarette, Halogen, low toxicity.External insulation material of the invention is added to organic/inorganic etc. in polymeric substrate Anti-irradiation agent, the effective destruction for inhibiting gamma-radiation under nuclear environment, reduce the intermolecular C-C key of polymer material because by Excitation and caused by chain be broken, extend material service life under nuclear environment, the core prepared using external insulation material of the invention The external insulation layer of electric K1 class cable passes through 1-10kGy/h, intergal dose 2400kGy60It can still keep preferable after the irradiation of Co gamma-radiation Elongation at break.High efficiency composition antioxidant is introduced in material prescription simultaneously, has obstructed free radical as intermediary and polymerization Object generates new free radical, to control degradation rate, calculates that material can be at a temperature of 90 DEG C by Arrhenius equation It uses 70 years or more.
In nuclear island provided by the invention in halogen-free flameproof outer insulating material, anti-aging agent and composite antioxidant addition can delay or The progress for inhibiting polymer oxidation process, to prevent the aging of polymer and prolong its service life；Anti-irradiation agent addition can Various rays are absorbed, material Antiradiation service life is improved；Crosslinking sensitizer effect reduces material irradiation dosage, improves production Efficiency.
Anti-aging agent and composite antioxidant cooperate, used above using 70 years at a temperature of so that this patent material is had 90 DEG C Service life；A variety of anti-irradiation agents and the addition such as a large amount of fire retardants and pin fumicants, final material of the present invention has high radiation resistance, and (γ is penetrated Line, >=2400kGy) and good flame retardant property (insulation core wire is burnt by single vertical), and the property such as low cigarette, Halogen, low toxicity Energy.
Nuclear island inner cable halogen-free flameproof external insulation layer material provided by the invention is using use in the nuclear island of crosslinking with radiation mode Cable halogen-free flameproof external insulation material, performance meet extra long life (90 DEG C, >=70 years) and use, and insulating layer passes through single vertical burning And high radiation resistance (gamma-rays, >=2400kGy).
In preparation method provided by the invention, traditional mixing is substituted using mixer+bis- ranks double-screw extruding pelletizing technique The material mixing of machine+single screw rod extruding and pelletizing process, preparation is more uniform, and performance is more stable.
Specific embodiment
The present invention is further illustrated below by the mode of embodiment, but does not therefore limit the present invention to the reality It applies among a range.In the following examples, the experimental methods for specific conditions are not specified, according to conventional methods and conditions, or according to quotient The selection of product specification.
Embodiment 1
Raw material:
Operating procedure:
By low density polyethylene (LDPE) (LDPE), ultra-low density polyethylene (VLDPE) ethylene propylene diene rubber (EPDM), anti-aging agent RD, antioxidant 1010, anti-oxidant DLTP, ultraviolet (UV) 328, zinc stearate, pin fumicants ammonium octamolybdate, boron nitride, magnesium hydroxide, Zinc borate, hypo-aluminum orthophosphate, hexaphenoxycyclotriphosphazene and environment-friendly red master batch are put into 75 liters of mixers, to 130 after melting DEG C or so be kneaded 5 minutes, crosslinking sensitizer TAIC and anti-irradiation agent A high phenyl siloxane rubber (phenyl content 40%) is then added, It is kneaded 5-10 minutes, is then lifted out to dual-band twin-screw extruder, in 120-160 DEG C of temperature in 130-150 DEG C of temperature range Air-cooled extruding pelletization in range.
Embodiment 2
Raw material:
Operating procedure:
Low density polyethylene (LDPE) (LDPE), ultra-low density polyethylene (VLDPE) ethylene propylene diene rubber (EPDM), ethylene-is pungent Alkene copolymer (POE), anti-aging agent RD, antioxidant 1010, anti-oxidant DLTP, ultraviolet (UV) 328, zinc stearate, pin eight molybdenum of fumicants Sour ammonium, boron nitride, magnesium hydroxide, zinc borate, hypo-aluminum orthophosphate, hexaphenoxycyclotriphosphazene and environment-friendly red master batch are put into 75 liters In mixer, it is kneaded 5 minutes after melting to 130 DEG C or so, crosslinking sensitizer TAIC and anti-irradiation agent A high phenyl silicon is then added Rubber (phenyl content 40%) is kneaded 5-10 minutes in 130-150 DEG C of temperature range, is then lifted out to double rank twin-screw extrusions Machine, the air-cooled extruding pelletization in 120-160 DEG C of temperature range.
Embodiment 3
Raw material:
Operating procedure:
Low density polyethylene (LDPE) (LDPE), ultra-low density polyethylene (VLDPE) ethylene propylene diene rubber (EPDM), ethylene-is pungent Alkene copolymer (POE), anti-aging agent RD, antioxidant 1010, anti-oxidant DLTP, ultraviolet (UV) 328, zinc stearate, pin eight molybdenum of fumicants Sour ammonium, boron nitride, magnesium hydroxide, zinc borate, hypo-aluminum orthophosphate, hexaphenoxycyclotriphosphazene and environment-friendly red master batch are put into 75 liters In mixer, it is kneaded 5 minutes after melting to 130 DEG C or so, crosslinking sensitizer TAIC and anti-irradiation agent A high phenyl silicon is then added Rubber (phenyl content 40%) is kneaded 5-10 minutes in 130-150 DEG C of temperature range, is then lifted out to double rank twin-screw extrusions Machine, the air-cooled extruding pelletization in 120-160 DEG C of temperature range.
Embodiment 4
Raw material:
Operating procedure:
Low density polyethylene (LDPE) (LDPE), ultra-low density polyethylene (VLDPE) ethylene propylene diene rubber (EPDM), ethylene-is pungent Alkene copolymer (POE), anti-aging agent RD, antioxidant 1010, anti-oxidant DLTP, ultraviolet (UV) 328, zinc stearate, pin eight molybdenum of fumicants Sour ammonium, boron nitride, magnesium hydroxide, zinc borate, hypo-aluminum orthophosphate, hexaphenoxycyclotriphosphazene and environment-friendly red master batch are put into 75 liters In mixer, it is kneaded 5 minutes after melting to 130 DEG C or so, crosslinking sensitizer TAIC and anti-irradiation agent A high phenyl silicon is then added Rubber (phenyl content 40%) is kneaded 5-10 minutes in 130-150 DEG C of temperature range, is then lifted out to double rank twin-screw extrusions Machine, the air-cooled extruding pelletization in 120-160 DEG C of temperature range.
Embodiment 5
Raw material:
Operating procedure:
Low density polyethylene (LDPE) (LDPE), ultra-low density polyethylene (VLDPE) ethylene propylene diene rubber (EPDM), ethylene-is pungent Alkene copolymer (POE), anti-aging agent RD, antioxidant 1010, anti-oxidant DLTP, ultraviolet (UV) 328, zinc stearate, pin eight molybdenum of fumicants Sour ammonium, boron nitride, magnesium hydroxide, zinc borate, hypo-aluminum orthophosphate, hexaphenoxycyclotriphosphazene and environment-friendly red master batch are put into 75 liters In mixer, it is kneaded 5 minutes after melting to 130 DEG C or so, crosslinking sensitizer TAIC and anti-irradiation agent A high phenyl silicon is then added Rubber (phenyl content 40%) is kneaded 5-10 minutes in 130-150 DEG C of temperature range, is then lifted out to double rank twin-screw extrusions Machine, the air-cooled extruding pelletization in 120-160 DEG C of temperature range.
Embodiment 6
Raw material:
Operating procedure:
Low density polyethylene (LDPE) (LDPE), ultra-low density polyethylene (VLDPE) ethylene propylene diene rubber (EPDM), ethylene-is pungent Alkene copolymer (POE), anti-aging agent RD, antioxidant 1010, anti-oxidant DLTP, ultraviolet (UV) 328, zinc stearate, pin eight molybdenum of fumicants Sour ammonium, boron nitride, magnesium hydroxide, zinc borate, hypo-aluminum orthophosphate, hexaphenoxycyclotriphosphazene and environment-friendly red master batch are put into 75 liters In mixer, it is kneaded 5 minutes after melting to 130 DEG C or so, crosslinking sensitizer TAIC and anti-irradiation agent A high phenyl silicon is then added Rubber (phenyl content 40%) is kneaded 5-10 minutes in 130-150 DEG C of temperature range, is then lifted out to double rank twin-screw extrusions Machine, the air-cooled extruding pelletization in 120-160 DEG C of temperature range.
Embodiment 7
Raw material:
Operating procedure:
Low density polyethylene (LDPE) (LDPE), ultra-low density polyethylene (VLDPE) ethylene propylene diene rubber (EPDM), ethylene-is pungent Alkene copolymer (POE), anti-aging agent RD, antioxidant 1010, anti-oxidant DLTP, ultraviolet (UV) 328, zinc stearate, pin eight molybdenum of fumicants Sour ammonium, boron nitride, magnesium hydroxide, zinc borate, hypo-aluminum orthophosphate, hexaphenoxycyclotriphosphazene and environment-friendly red master batch are put into 75 liters In mixer, it is kneaded 5 minutes after melting to 130 DEG C or so, crosslinking sensitizer TAIC and anti-irradiation agent A high phenyl silicon is then added Rubber (phenyl content 40%) is kneaded 5-10 minutes in 130-150 DEG C of temperature range, is then lifted out to double rank twin-screw extrusions Machine, the air-cooled extruding pelletization in 120-160 DEG C of temperature range.
Embodiment 8
Raw material:
Operating procedure:
Low density polyethylene (LDPE) (LDPE), ultra-low density polyethylene (VLDPE) ethylene propylene diene rubber (EPDM), ethylene-is pungent Alkene copolymer (POE), anti-aging agent RD, antioxidant 1010, anti-oxidant DLTP, ultraviolet (UV) 328, zinc stearate, pin eight molybdenum of fumicants Sour ammonium, boron nitride, magnesium hydroxide, zinc borate, hypo-aluminum orthophosphate, hexaphenoxycyclotriphosphazene and environment-friendly red master batch are put into 75 liters In mixer, it is kneaded 5 minutes after melting to 130 DEG C or so, crosslinking sensitizer TAIC and anti-irradiation agent A high phenyl silicon is then added Rubber (phenyl content 40%) is kneaded 5-10 minutes in 130-150 DEG C of temperature range, is then lifted out to double rank twin-screw extrusions Machine, the air-cooled extruding pelletization in 120-160 DEG C of temperature range.
Embodiment 9
Raw material:
Operating procedure:
Low density polyethylene (LDPE) (LDPE), ultra-low density polyethylene (VLDPE) ethylene propylene diene rubber (EPDM), ethylene-is pungent Alkene copolymer (POE), anti-aging agent RD, antioxidant 1010, anti-oxidant DLTP, ultraviolet (UV) 328, zinc stearate, pin eight molybdenum of fumicants Sour ammonium, boron nitride, magnesium hydroxide, zinc borate, hypo-aluminum orthophosphate, hexaphenoxycyclotriphosphazene and environment-friendly red master batch are put into 75 liters In mixer, it is kneaded 5 minutes after melting to 130 DEG C or so, crosslinking sensitizer TMPTMA and anti-irradiation agent A high phenyl is then added Silicon rubber (phenyl content 40%) is kneaded 5-10 minutes in 130-150 DEG C of temperature range, is then lifted out to double rank twin-screws and is squeezed Machine out, the air-cooled extruding pelletization in 120-160 DEG C of temperature range.
Embodiment 10
Raw material:
Operating procedure:
Low density polyethylene (LDPE) (LDPE), ultra-low density polyethylene (VLDPE) ethylene propylene diene rubber (EPDM), ethylene-is pungent Alkene copolymer (POE), anti-aging agent RD, antioxidant 1010, anti-oxidant DLTP, ultraviolet (UV) 328, zinc stearate, pin eight molybdenum of fumicants Sour ammonium, boron nitride, magnesium hydroxide, zinc borate, hypo-aluminum orthophosphate, hexaphenoxycyclotriphosphazene, phenoxy group polyphosphazene and environment-friendly type yellow Masterbatch is put into 75 liters of mixers, after melting to 130 DEG C or so be kneaded 5 minutes, then be added crosslinking sensitizer TMPTMA and Anti-irradiation agent A high phenyl siloxane rubber (phenyl content 40%) is kneaded 5-10 minutes in 130-150 DEG C of temperature range, then mentions Dual-band twin-screw extruder is risen to, the air-cooled extruding pelletization in 120-160 DEG C of temperature range.
Embodiment 11
Raw material:
Operating procedure:
Low density polyethylene (LDPE) (LDPE), ultra-low density polyethylene (VLDPE) ethylene propylene diene rubber (EPDM), ethylene-is pungent Alkene copolymer (POE), anti-aging agent RD, antioxidant 1010, anti-oxidant DLTP, ultraviolet (UV) 328, zinc stearate, pin eight molybdenum of fumicants Sour ammonium, boron nitride, magnesium hydroxide, zinc borate, hypo-aluminum orthophosphate, hexaphenoxycyclotriphosphazene, phenoxy group polyphosphazene and environment-friendly type yellow Masterbatch is put into 75 liters of mixers, after melting to 130 DEG C or so be kneaded 5 minutes, then be added crosslinking sensitizer TMPTMA and Anti-irradiation agent A high phenyl siloxane rubber (phenyl content 40%) is kneaded 5-10 minutes in 130-150 DEG C of temperature range, then mentions Dual-band twin-screw extruder is risen to, the air-cooled extruding pelletization in 120-160 DEG C of temperature range.
Embodiment 12
Raw material:
Operating procedure:
Low density polyethylene (LDPE) (LDPE), ultra-low density polyethylene (VLDPE) ethylene propylene diene rubber (EPDM), ethylene-is pungent Alkene copolymer (POE), anti-aging agent RD, antioxidant 1010, anti-oxidant DLTP, ultraviolet (UV) 328, zinc stearate, pin eight molybdenum of fumicants Sour ammonium, boron nitride, magnesium hydroxide, zinc borate, hypo-aluminum orthophosphate, hexaphenoxycyclotriphosphazene, phenoxy group polyphosphazene and environment-friendly type yellow Masterbatch is put into 75 liters of mixers, is kneaded 5 minutes after melting to 130 DEG C or so, and crosslinking sensitizer TMPTMA is then added, resists Agent A high phenyl siloxane rubber (phenyl content 40%) and phenylene silicone rubber (penylene content is 60%) are irradiated, in 130-150 DEG C of temperature It is kneaded 5-10 minutes, is then lifted out to dual-band twin-screw extruder in range, air-cooled extrusion is made in 120-160 DEG C of temperature range Grain.
Embodiment 13
Raw material:
Operating procedure:
Low density polyethylene (LDPE) (LDPE), ultra-low density polyethylene (VLDPE) ethylene propylene diene rubber (EPDM), ethylene-is pungent Alkene copolymer (POE), anti-aging agent RD, antioxidant 1010, anti-oxidant DLTP, ultraviolet (UV) 328, zinc stearate, pin eight molybdenum of fumicants Sour ammonium, boron nitride, magnesium hydroxide, zinc borate, hypo-aluminum orthophosphate, hexaphenoxycyclotriphosphazene, phenoxy group polyphosphazene and environment-friendly type yellow Masterbatch is put into 150 liters of mixers, after melting to 130 DEG C or so be kneaded 5 minutes, then be added crosslinking sensitizer TMPTMA and Anti-irradiation agent A high phenyl siloxane rubber (phenyl content 40%) is kneaded 5-10 minutes in 130-150 DEG C of temperature range, then mentions Dual-band twin-screw extruder is risen to, the air-cooled extruding pelletization in 120-160 DEG C of temperature range.
Embodiment 14
Raw material:
Operating procedure:
Low density polyethylene (LDPE) (LDPE), ultra-low density polyethylene (VLDPE) ethylene propylene diene rubber (EPDM), ethylene-is pungent Alkene copolymer (POE), anti-aging agent RD, antioxidant 1010, anti-oxidant DLTP, ultraviolet (UV) 328, zinc stearate, pin eight molybdenum of fumicants Sour ammonium, boron nitride, magnesium hydroxide, zinc borate, hypo-aluminum orthophosphate, hexaphenoxycyclotriphosphazene, phenoxy group polyphosphazene and environment-friendly type yellow Masterbatch is put into 200 liters of mixers, after melting to 130 DEG C or so be kneaded 5 minutes, then be added crosslinking sensitizer TMPTMA and Anti-irradiation agent A high phenyl siloxane rubber (phenyl content 40%) is kneaded 5-10 minutes in 130-150 DEG C of temperature range, then mentions Dual-band twin-screw extruder is risen to, the air-cooled extruding pelletization in 120-160 DEG C of temperature range.
Application Example
By the high radiation resistance nuclear island inner cable halogen-free flameproof external insulation material of the extra long life of embodiment 1-14, by GB/ T12706.1-2008 cable production method, with nuclear island inner cable Halogen interior insulation material in φ 30-45 (interior insulation)/φ 45-90 (external insulation) two single screw extrusion machines melt double-layer coextrusion at a temperature of 120-160 DEG C and go out, and conductor is flat for single 1.5/2.5 Side, insulating layer overall thickness 0.8mm, wherein inner insulating layer thickness 0.15-0.2mm, external insulation layer thickness 0.6-0.65mm, outside cable Diameter 3.4mm, the insulating layer pass through electron accelerator crosslinking with radiation, dosage 150-200kGy.
The high radiation resistance nuclear island inner cable halogen-free flameproof external insulation material of extra long life of the invention and its cable performance of preparation It is shown in Table.
Table 1: the test method and standard of each test item:
Table 2: external insulation material and cable performance
Table 2 (continuous 1)
Table 2 (continuous 2)
Pass through halogen-free flameproof external insulation material in the high radiation resistance nuclear island of the extra long life for preparing the embodiment of the present invention 1-12 And its insulated cable performance obtained is compared it can be concluded that following result:
(1) embodiment 1 and embodiment 2 are formulated, in addition to embodiment 2 increases ethylene-octene copolymer (POE) in substrate, Other formulas are consistent, and the intensity of PERFORMANCE EXAMPLES 1 is lower than embodiment 2, and elongation is higher than embodiment 2, other performances are protected substantially It holds unanimously, therefore, it can be seen that the present invention is able to ascend material tensile strength by the way that ethylene-octene copolymer (POE) is added, together When have and suitably reduce material elongation at break, but overall applicability performance is improved.
(2) embodiment 2 and embodiment 3 are formulated, and substrate type is consistent, and embodiment 3 increases ultra-low density polyethylene (VLDPE) 5kg reduces low density polyethylene (LDPE) (LDPE) 5kg, other formulas are consistent, and the strength elongation of PERFORMANCE EXAMPLES 3 is above Embodiment 2, other performances are consistent substantially, show that ultra-low density polyethylene (VLDPE) is added to material tensile after the present invention Intensity and elongation are improved, but ultra-low density polyethylene (VLDPE) price is higher than low density polyethylene (LDPE) (LDPE).
(3) embodiment 3 and embodiment 4 are formulated, and formula components are consistent, antioxidant 1010 and antioxidant in embodiment 3 DLTP dosage is consistent, and antioxidant 1010 is consistent with the total dosage of DLTP in embodiment 4, but DLTP dosage is more than 1010, aging It can be consistent substantially, obtain old to material when antioxidant dosage DLTP:1010 is greater than 1:1 also superior to embodiment 3, other performances Change performance to be obviously improved, the two synergy is promoted.
(4) embodiment 4 and embodiment 5 are formulated, and formula components are consistent, and UV328 dosage is more than embodiment in embodiment 5 4,5 anti-radiation performance of embodiment is slightly better than embodiment 4, other performances are consistent substantially, show that the introducing of UV328 is able to ascend Material anti-radiation performance.
(5) embodiment 5 and embodiment 6 are formulated, and formula components are consistent, and zinc borate flame retardant is than implementing in embodiment 6 More 2.5kg in example 5, and hypo-aluminum orthophosphate lacks 2.5kg, 6 intensity of embodiment is higher than, stretches rate lower than embodiment 5,6 oxygen index (OI) of embodiment It is below embodiment 5 with smoke density, other performances are consistent substantially, show that the introducing of hypo-aluminum orthophosphate improves flame retardant property, But smoke density is larger, and the density of hypo-aluminum orthophosphate is far below zinc borate, affects the strength of materials, therefore pass through hypo-aluminum orthophosphate and boron The coordinated of sour zinc has obtained suitable flame retardant effect and smoke density effect.
(6) embodiment 7 and embodiment 8 are formulated, and formula components are consistent, and fire retardant magnesium hydroxide increases in embodiment 8 5kg, intensity are stretched the performances such as rate and are mostly declined slightly than embodiment 7, but multipotency meets standard requirements, and prepared by embodiment 7 Insulated electric conductor, can by 2.5 squares or more flame-retardancy requirements, but cannot by 1.5 squares or less small dimension electric wire flame-retardancy requirements, and Embodiment 7 increases magnesium hydroxide additive amount, can meet all insulated electric conductor flame retardant properties, other performances are also able to satisfy standard.
(7) embodiment 8 and embodiment 9 are formulated, and crosslinking agent trimethylol-propane trimethacrylate is used in embodiment 9 (TMPTMA) crosslinking agent triallyl isocyanurate (TAIC) in alternate embodiment 8, performance is consistent substantially, obtains two A crosslinking action is suitable.
(8) embodiment 9 and embodiment 10 are formulated, with environmental protection in environment-friendly type yellow Masterbatch alternate embodiment 9 in embodiment 10 Outside type red master batch, other than color is different, performance is consistent substantially, show that different Masterbatch do not have direct shadow to material It rings.
(9) embodiment 10 and embodiment 11 are formulated, with inorganic anti-irradiation agent boron carbide alternate embodiment 10 in embodiment 11 In inorganic anti-irradiation agent boron nitride, performance is consistent substantially, show that two kinds of inorganic anti-irradiation agent performances are suitable.
(10) embodiment 11 and embodiment 12 are formulated, and increase organic anti-irradiation agent phenylene silicone rubber (benzene in embodiment 12 Content is supportted as 60%) 0.5kg, reduces the high phenyl siloxane rubber of organic anti-irradiation agent (phenyl content 40%) 0.5kg, other formulas Ingredient is identical, and 12 radiation-resistant property of embodiment is better than embodiment 11, obtains phenylene silicone rubber (penylene content is 60%) Flouride-resistani acid phesphatase Performance is better than high phenyl siloxane rubber (phenyl content 40%), therefore can improve anti-radiation performance by above combination.

Claims (14)

1. a kind of nuclear island inner cable halogen-free flameproof outer insulating material, which is characterized in that it includes the raw material of following parts by weight meter: poly- Close 90-112 parts of object substrate；60-80 parts of inorganic fire retardants；10-20 parts of zinc borate；8-12 parts of polyphosphazene flame retardant；The resistance of phosphorus nitrogen system Agent 10-20 parts of combustion；Fumicants 1-3 parts of pin；1-3 parts of anti-aging agent；4-8 parts of composite antioxidant；3-8 parts of anti-irradiation agent: processing aid 5- 10 parts；
Wherein, the polymeric substrate includes low density polyethylene (LDPE), ultra-low density polyethylene, ethylene propylene diene rubber and ethylene- Octene copolymer；The processing aid includes crosslinking sensitizer and lubricant.
2. nuclear island inner cable halogen-free flameproof outer insulating material according to claim 1, which is characterized in that the compound antioxygen Agent includes primary antioxidant, auxiliary antioxidant and ultraviolet absorbing agent.
3. nuclear island inner cable halogen-free flameproof outer insulating material according to claim 2, which is characterized in that the primary antioxidant Including pentaerythritol ester and/or β-(3,5- di-tert-butyl -4- hydroxy phenyl) propionic acid octadecyl ester；The auxiliary antioxidant includes sulphur Esters antioxidant；The ultraviolet absorbing agent includes 2- (bis- tertiary amyl phenyl of 2'- hydroxyl -3', 5'-) benzotriazole, 2- (2'- Hydroxyl -5'- spy octyl phenyl) benzotriazole or 2- (bis- (a, a- dimethyl benzyl) phenyl of 2'- hydroxyl -3', 5'-) benzotriazole One or more of.
4. nuclear island inner cable halogen-free flameproof outer insulating material according to claim 1, which is characterized in that the anti-irradiation agent Including anti-irradiation agent A and anti-irradiation agent B, wherein anti-irradiation agent A is high phenyl siloxane rubber and/or phenylene silicone rubber；Anti-irradiation agent B For boron carbide and/or boron nitride.
5. nuclear island inner cable halogen-free flameproof outer insulating material according to claim 1, which is characterized in that the crosslinking sensitization Agent includes trimethylol-propane trimethacrylate and/or iso-cyanuric acid triallyl ester, and the lubricant includes poly- second One or more of alkene wax, zinc stearate or calcium stearate.
6. nuclear island inner cable halogen-free flameproof outer insulating material according to claim 1, which is characterized in that the low-density Polyethylene, ultra-low density polyethylene, ethylene propylene diene rubber and ethylene-octene copolymer mass ratio be 50-60:20-30:10- 15:10-15。
7. nuclear island inner cable halogen-free flameproof outer insulating material according to claim 2, which is characterized in that the main antioxygen The mass ratio of the additive amount of agent, auxiliary antioxidant and ultraviolet absorbing agent is 1:1-3:0.1-0.5.
8. nuclear island inner cable halogen-free flameproof outer insulating material according to claim 4, which is characterized in that the Flouride-resistani acid phesphatase The addition mass ratio of agent A and anti-irradiation agent B is 3-4:1-2.
9. nuclear island inner cable halogen-free flameproof outer insulating material according to claim 1, which is characterized in that the crosslinking sensitization The mass ratio of agent and lubricant is 1:1-2.
10. nuclear island inner cable halogen-free flameproof outer insulating material according to claim 1, which is characterized in that the processing Auxiliary agent further includes environment-friendly type Masterbatch.
11. the preparation method of nuclear island inner cable halogen-free flameproof outer insulating material as claimed in claim 4, which is characterized in that will gather Close object substrate, inorganic fire retardants, zinc borate, polyphosphazene flame retardant, phosphorus-nitrogen containing flame retardant, anti-aging agent, pin fumicants, compound antioxygen Agent, anti-irradiation agent B and lubricant are put into mixer and are kneaded, and are kneaded 5 minutes after melting to 130 DEG C or so, crosslinking is then added Sensitizer and anti-irradiation agent A are kneaded 5-10 minutes in 130-150 DEG C of temperature range, are then lifted out to double rank twin-screw extrusions Machine, the air-cooled extruding pelletization in 120-160 DEG C of temperature range.
12. a kind of nuclear island inner cable halogen-free flameproof external insulation layer material, which is characterized in that its raw material includes that claim 1-10 appoints Nuclear island inner cable halogen-free flameproof outer insulating material described in one.
13. the preparation method of nuclear island inner cable halogen-free flameproof external insulation layer material described in claim 12, which is characterized in that will The nuclear island inner cable halogen-free flameproof outer insulating material and nuclear island inner cable Halogen interior insulation material exist in two single screw extrusion machines Double-layer coextrusion is melted at a temperature of 120-160 DEG C to go out, and is coated on copper conductor, crosslinking with radiation.
14. the preparation method of nuclear island inner cable halogen-free flameproof external insulation layer material according to claim 13, feature exist In the radiation source of the crosslinking with radiation is electron beam, irradiation dose 150-200KGy.
CN201811305098.6A 2018-11-02 2018-11-02 Nuclear island inner cable halogen-free flameproof external insulation material, cable outer insulation and preparation method Pending CN109438813A (en)

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