CN109575409A - Nuclear island inner cable halogen-free flameproof jacket material, cable jacket layer and preparation method - Google Patents
Nuclear island inner cable halogen-free flameproof jacket material, cable jacket layer and preparation method Download PDFInfo
- Publication number
- CN109575409A CN109575409A CN201811299995.0A CN201811299995A CN109575409A CN 109575409 A CN109575409 A CN 109575409A CN 201811299995 A CN201811299995 A CN 201811299995A CN 109575409 A CN109575409 A CN 109575409A
- Authority
- CN
- China
- Prior art keywords
- agent
- free flameproof
- nuclear island
- inner cable
- halogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0869—Acids or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/387—Borates
-
- 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
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
-
- 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
Abstract
The invention discloses a kind of nuclear island inner cable halogen-free flameproof jacket material, cable jacket layer and preparation methods.The nuclear island inner cable halogen-free flameproof oversheath 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 that polymeric substrate, inorganic fire retardants, zinc borate, polyphosphazene flame retardant, phosphorus-nitrogen containing flame retardant, anti-aging agent, composite antioxidant, anti-irradiation agent, lubricant and environment-friendly type Masterbatch are put into mixer and are kneaded, and is then lifted out to the air-cooled extruding pelletization of dual-band twin-screw extruder.Protective cover material of the invention has extra long life (90 DEG C >=70 years), high radiation resistance (gamma-rays, >=2400kGy), good electrical performance (>=3670M Ω cm), good flame retardant property (cable is burnt by A/B class bunchy), and low cigarette, Halogen, low toxicity.
Description
Technical field
The invention belongs to nuclear island inner cable protective cover material fields, and in particular to a kind of nuclear island inner cable halogen-free flameproof oversheath material
Material, cable jacket layer and preparation method thereof.
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 conventional nuclear cable sheath material generallys use vinyl-vinyl acetate copolymer (EVA) material
Expect, the vinyl acetate-CH in EVA material2CHCOOCH3Under long term heat ageing effect and under a large amount of radiation exposures, work is generated
Free love base (COO-) or active ion, and meeting further occurrence chemical reaction, living radical or active ion cause big point
Degradation reaction, cross-linking reaction, oxidation reaction and the molecular isomerism of subchain react, these reactions add material molecule reaction rate
Fastly, sheath material can become fragile, mechanical degradation, and the elongation at break of especially material declines to a great extent, and influence materials'use.
A seed nucleus electricity consumption cable Halogen-free flame retardant sheath material, specific formula disclosed in Chinese patent (CA102875947B) are as follows: poly-
Conjunction object substrate: 100 parts；Inorganic fire retardants: 100-140 parts；Polyphosphazene flame retardant: 15-25 parts；Nitrogenated flame retardant: 15-30；It is multiple
Conjunction antioxidant: 4-8 parts；Anti-irradiation agent: 5-15 parts；Processing aid: 6-12 parts；Polymeric substrate includes radiation grafting maleic anhydride
Ethylene-vinyl acetate copolymer and ethylene methyl methacrylate copolymer, the protective cover material superior performance, have it is good
Flame retardant property, stable radiation-resistant property, electric property and mechanical performance, and low cigarette, Halogen, low toxicity.The protective cover material has
Three generations's nuclear power 60 years service lifes and the gamma-rays of resistance to 1500kGy.
The proprietary material is added to a large amount of fire retardants, total amount is inorganic fire retardants: 100- to meet cable flame retardance
140 parts；Polyphosphazene flame retardant: 15-25 parts；Nitrogenated flame retardant: 15-30；Affect the mechanical property of materials, while the total agent of radiation resistance
Amount is 1500kGy, is not able to satisfy such as three generations's nuclear power AP1000 radiation resistance dosage 2000kGy requirements above.
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,.
Document " research of AP1000 npp safety shell inner cable qualification test ", the electrical 2016NO.4 of electrician, three generations's nuclear power
AP1000 radiation resistance: nominal situation gamma-rays adds up irradiation dose 231kGy (containing 10% allowance), the accumulative irradiation of gamma-rays under DBA
Dosage 429kGy (contains 10% allowance), β x ray irradiation x accumulated dose 2970kGy (containing 10% allowance), 2970kGy β ray etc. under DBA
It imitates to gamma-rays 1650kGy, accumulated dose 231+429+1650=2309kGy.
The document has determined that three generations's nuclear power AP1000 nuclear power nuclear island inner cable total dose is 2309kGy, but makes at present
Three generations's nuclear power cable sheath material radiation resistance dosage can only meet certain three generations's nuclear power cables usually in 1500kGy or so
Demand is not able to satisfy all three generations's nuclear power cable demands.
Summary of the invention
Technical problem to be solved by the present invention lies in overcome existing sheath material heat ageing and radioresistance that can expire
The defects of all three generations's nuclear power cable sheaths of foot require, halogen-free flameproof performance is not ideal enough, provides in nuclear island and is hindered with cable Halogen
Fire the preparation method and application of oversheath material, cable jacket layer, the protective cover material have extra long life (90 DEG C, >=70 years, high resistance to
Irradiation behaviour (gamma-rays, >=2400kGy), restrictive coating are burnt A/B class by bunchy, 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 jacket material, and the material is former
Material includes following component in parts by weight: 80-112 parts of polymeric substrate；80-100 parts of inorganic fire retardants；Zinc borate 15-25
Part；8-12 parts of polyphosphazene flame retardant；8-12 parts of phosphorus-nitrogen containing flame retardant；1-3 parts of anti-aging agent；1-3 parts of smoke of gunpowder agent；Composite antioxidant 4-
8 parts；3-8 parts of anti-irradiation agent；6-12 parts of processing aid；
Wherein, the polymeric substrate includes the ethylene-vinyl acetate copolymer (EVA- of radiation grafting maleic anhydride
G-MAH), ethylene-vinyl acetate copolymer (EVA), ethylene-octene copolymer (POE) or ethylene methyl methacrylate are total
The combination of one or more of polymers (EMMA).
The inorganic fire retardants includes magnesium hydroxide.
The anti-aging agent is anti-aging agent RD.
The smoke of gunpowder agent is ammonium octamolybdate.
The polyphosphazene flame retardant includes hexaphenoxycyclotriphosphazene and/or the poly- polyphosphazene of phenoxy group.
Preferably, the mass ratio of the poly- polyphosphazene of hexaphenoxycyclotriphosphazene and phenoxy group is 8-12:0-4.
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.
Preferably, the sulphur ester antioxidant is dilauryl thiodipropionate and/or the double octadecyl esters of thio-2 acid.
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.
Preferably, the mass ratio of the additive amount of the primary antioxidant, auxiliary antioxidant, ultraviolet absorbing agent is 1:1-3:
0.1-0.7。
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；
Preferably, the mass ratio of the anti-irradiation agent A and anti-irradiation agent B is 3-4:1-2；
Preferably, the high phenyl siloxane rubber phenyl content is 40%.
More preferably, the penylene base silicon rubber penylene content is 60%, phenyl content 30%.
The processing aid includes crosslinking sensitizer and lubricant；
Preferably, the crosslinking sensitizer includes that trimethylol-propane trimethacrylate and/or triallyl are different
Cyanurate, the lubricant include the combination of one or more of polyethylene wax, zinc stearate or calcium stearate.
Preferably, the mass ratio of the crosslinking sensitizer and lubricant is 1-2:1.5-4.
More preferably, the processing aid further includes environment-friendly type Masterbatch；Crosslinking sensitizer, lubricant and the environmental protection
The mass ratio of type Masterbatch is 1-2:1.5-4:1.5-4.
Wherein, the ingredient of above-mentioned substance and content are as previously described.
Preferably, the polymeric substrate is the ethene-vinyl acetate of radiation grafting maleic anhydride in the present invention
Ester copolymer (EVA-g-MAH), ethylene-vinyl acetate copolymer (EVA), ethylene-octene copolymer (POE) and ethylene-first
Base methyl acrylate copolymer (EMMA), the ethylene-vinyl acetate copolymer (EVA-g-MAH) of radiation grafting maleic anhydride,
Ethylene-vinyl acetate copolymer (EVA), ethylene-octene copolymer (POE) and ethylene methyl methacrylate copolymer
(EMMA) weight fraction ratio is 5-15:10-30:5-15:60-80.
More preferably, in the ethylene-vinyl acetate copolymer (EVA) VA content in 14-40%；Ethylene-methyl-prop
MMA content is in 14%-40% in e pioic acid methyl ester copolymer (EMMA)；More preferably, the melt index MI of EVA and EMMA is 2-6.
The two of technical solution of the present invention are to provide the nuclear island inner cable halogen-free flameproof jacket material described in more than one
Preparation method, by polymeric substrate, inorganic fire retardants, zinc borate, polyphosphazene flame retardant, phosphorus-nitrogen containing flame retardant, anti-aging agent, multiple
It closes antioxidant, anti-irradiation agent B, lubricant and environment-friendly type Masterbatch to be put into mixer and be kneaded, be kneaded after melting to 130 DEG C or so
5 minutes, crosslinking sensitizer and anti-irradiation agent A is then added, 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.
The two of technical solution of the present invention are to provide a kind of nuclear island inner cable halogen-free flameproof external sheath layer, and raw material includes
Nuclear island inner cable halogen-free flameproof jacket material described in any of the above item.
The preparation method of above-described nuclear island inner cable halogen-free flameproof external sheath layer, will be outside nuclear island inner cable halogen-free flameproof
By single screw extrusion machine, melting extrusion under the conditions of 120-160 DEG C is coated on the double hyer insulation that crosslinking with radiation is crossed to sheath material
It core wire and has coated on halogen-free flameproof filled layer cable, crosslinking with radiation.The radiation source of the crosslinking with radiation is electron beam, institute
The irradiation dose 150-200KGy for the radiation stated.
The above specific method and examination criteria 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 oversheath material has stable radiation-resistant property, good anti-flammability in nuclear island produced by the present invention
Can, and low cigarette, Halogen, low toxicity.Oversheath material of the invention is added to the anti-irradiation agents such as organic/inorganic in polymeric substrate,
The effective destruction for inhibiting gamma-radiation under nuclear environment, reduces the intermolecular C-C key of polymer material and causes because being stimulated
Chain fracture, extend material service life under nuclear environment, the nuclear power K1 class cable prepared using oversheath material of the invention
External sheath layer pass through 1-10kGy/h, intergal dose 2400kGy60Preferable extension at break can be still kept after the irradiation of Co gamma-radiation
Rate.High efficiency composition antioxidant is introduced in material prescription simultaneously, free radical has been obstructed and has been generated newly as intermediary and polymer
Free radical calculates by Arrhenius equation to control degradation rate, material can at a temperature of 90 DEG C using 70 years with
On.
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 polymer EVA-g-MAH, EVA, EMMA, anti-aging agent RD, antioxidant 1010, anti-oxidant DLTP, ultraviolet light
UV328, zinc stearate, smoke of gunpowder agent ammonium octamolybdate, boron carbide, magnesium hydroxide, zinc borate, hypo-aluminum orthophosphate, six phenoxy group rings, three phosphorus
Nitrile, phenoxy group polyphosphazene and environment-friendly black master batch are put into 75 liters of mixers, after melting to 130 DEG C or so be kneaded 5 minutes, so
Crosslinking sensitizer TMPTMA, anti-irradiation agent A high phenyl siloxane rubber (phenyl content 40%) and phenylene silicone rubber are added afterwards, and (penylene contains
Amount is 60%), to be kneaded 5-10 minutes, be then lifted out to dual-band twin-screw extruder, in 120- in 130-150 DEG C of temperature range
Air-cooled extruding pelletization in 160 DEG C of temperature ranges；
Embodiment 2
Raw material:
Operating procedure:
By polymer EVA-g-MAH, EVA, EMMA, anti-aging agent RD, antioxidant 1010, anti-oxidant DLTP, ultraviolet light
UV328, zinc stearate, smoke of gunpowder agent ammonium octamolybdate, boron carbide, magnesium hydroxide, zinc borate, hypo-aluminum orthophosphate, six phenoxy group rings, three phosphorus
Nitrile, phenoxy group polyphosphazene and environment-friendly black master batch are put into 75 liters of mixers, after melting to 130 DEG C or so be kneaded 5 minutes, so
Crosslinking sensitizer TMPTMA, anti-irradiation agent A high phenyl siloxane rubber (phenyl content 40%) and phenylene silicone rubber are added afterwards, and (penylene contains
Amount is 60%), to be kneaded 5-10 minutes, be then lifted out to dual-band twin-screw extruder, in 120- in 130-150 DEG C of temperature range
Air-cooled extruding pelletization in 160 DEG C of temperature ranges；
Embodiment 3
Raw material
Operating procedure:
By polymer EVA-g-MAH, EVA, POE, EMMA, anti-aging agent RD, antioxidant 1010, anti-oxidant DLTP, ultraviolet light
UV328, zinc stearate, smoke of gunpowder agent ammonium octamolybdate, boron carbide, magnesium hydroxide, zinc borate, hypo-aluminum orthophosphate, six phenoxy group rings, three phosphorus
Nitrile, phenoxy group polyphosphazene and environment-friendly black master batch are put into 75 liters of mixers, after melting to 130 DEG C or so be kneaded 5 minutes, so
Crosslinking sensitizer TMPTMA, anti-irradiation agent A high phenyl siloxane rubber (phenyl content 40%) and phenylene silicone rubber are added afterwards, and (penylene contains
Amount is 60%), to be kneaded 5-10 minutes, be then lifted out to dual-band twin-screw extruder, in 120- in 130-150 DEG C of temperature range
Air-cooled extruding pelletization in 160 DEG C of temperature ranges；
Embodiment 4
Raw material
Operating procedure:
By polymer EVA-g-MAH, EVA, POE, EMMA, anti-aging agent RD, antioxidant 1010, anti-oxidant DLTP, ultraviolet light
UV328, zinc stearate, smoke of gunpowder agent ammonium octamolybdate, boron carbide, magnesium hydroxide, zinc borate, hypo-aluminum orthophosphate, six phenoxy group rings, three phosphorus
Nitrile, phenoxy group polyphosphazene and environment-friendly black master batch are put into 75 liters of mixers, after melting to 130 DEG C or so be kneaded 5 minutes, so
Crosslinking sensitizer TMPTMA, anti-irradiation agent A high phenyl siloxane rubber (phenyl content 40%) and phenylene silicone rubber are added afterwards, and (penylene contains
Amount is 60%), to be kneaded 5-10 minutes, be then lifted out to dual-band twin-screw extruder, in 120- in 130-150 DEG C of temperature range
Air-cooled extruding pelletization in 160 DEG C of temperature ranges；
Embodiment 5
Raw material
Operating procedure:
By polymer EVA-g-MAH, EVA, POE, EMMA, anti-aging agent RD, antioxidant 1010, anti-oxidant DLTP, ultraviolet light
UV328, zinc stearate, smoke of gunpowder agent ammonium octamolybdate, boron carbide, magnesium hydroxide, zinc borate, hypo-aluminum orthophosphate, six phenoxy group rings, three phosphorus
Nitrile, phenoxy group polyphosphazene and environment-friendly black master batch are put into 75 liters of mixers, after melting to 130 DEG C or so be kneaded 5 minutes, so
Crosslinking sensitizer TMPTMA, anti-irradiation agent A high phenyl siloxane rubber (phenyl content 40%) and phenylene silicone rubber are added afterwards, and (penylene contains
Amount is 60%), to be kneaded 5-10 minutes, be then lifted out to dual-band twin-screw extruder, in 120- in 130-150 DEG C of temperature range
Air-cooled extruding pelletization in 160 DEG C of temperature ranges；
Embodiment 6
Raw material
Operating procedure:
By polymer EVA-g-MAH, EVA, POE, EMMA, anti-aging agent RD, antioxidant 1010, anti-oxidant DLTP, ultraviolet light
UV328, zinc stearate, smoke of gunpowder agent ammonium octamolybdate, boron carbide, magnesium hydroxide, zinc borate, hypo-aluminum orthophosphate, six phenoxy group rings, three phosphorus
Nitrile, phenoxy group polyphosphazene and environment-friendly black master batch are put into 75 liters of mixers, after melting to 130 DEG C or so be kneaded 5 minutes, so
Crosslinking sensitizer TMPTMA, anti-irradiation agent A high phenyl siloxane rubber (phenyl content 40%) and phenylene silicone rubber are added afterwards, and (penylene contains
Amount is 60%), to be kneaded 5-10 minutes, be then lifted out to dual-band twin-screw extruder, in 120- in 130-150 DEG C of temperature range
Air-cooled extruding pelletization in 160 DEG C of temperature ranges.
Embodiment 7
Raw material
Operating procedure:
By polymer EVA-g-MAH, EVA, POE, EMMA, anti-aging agent RD, antioxidant 1010, anti-oxidant DLTP, ultraviolet light
UV328, zinc stearate, smoke of gunpowder agent ammonium octamolybdate, boron carbide, magnesium hydroxide, zinc borate, hypo-aluminum orthophosphate, six phenoxy group rings, three phosphorus
Nitrile, phenoxy group polyphosphazene and environment-friendly black master batch are put into 75 liters of mixers, after melting to 130 DEG C or so be kneaded 5 minutes, so
Crosslinking sensitizer TMPTMA, anti-irradiation agent A high phenyl siloxane rubber (phenyl content 40%) and phenylene silicone rubber are added afterwards, and (penylene contains
Amount is 60%), to be kneaded 5-10 minutes, be then lifted out to dual-band twin-screw extruder, in 120- in 130-150 DEG C of temperature range
Air-cooled extruding pelletization in 160 DEG C of temperature ranges.
Embodiment 8
Raw material
Operating procedure:
By polymer EVA-g-MAH, EVA, POE, EMMA, anti-aging agent RD, antioxidant 1010, anti-oxidant DLTP, ultraviolet light
UV328, zinc stearate, smoke of gunpowder agent ammonium octamolybdate, boron carbide, magnesium hydroxide, zinc borate, hypo-aluminum orthophosphate, six phenoxy group rings, three phosphorus
Nitrile, phenoxy group polyphosphazene and environment-friendly black master batch are put into 110 liters of mixers, are kneaded 5 minutes after melting to 130 DEG C or so,
Then crosslinking sensitizer TMPTMA, anti-irradiation agent A high phenyl siloxane rubber (phenyl content 40%) and phenylene silicone rubber (penylene is added
Content is 60%), to be kneaded 5-10 minutes, be 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.
Embodiment 9
Raw material
Operating procedure:
By polymer EVA-g-MAH, EVA, POE, EMMA, anti-aging agent RD, antioxidant 1010, anti-oxidant DLTP, ultraviolet light
UV328, zinc stearate, smoke of gunpowder agent ammonium octamolybdate, boron carbide, magnesium hydroxide, zinc borate, hypo-aluminum orthophosphate, six phenoxy group rings, three phosphorus
Nitrile, phenoxy group polyphosphazene and environment-friendly black master batch are put into 150 liters of mixers, are kneaded 5 minutes after melting to 130 DEG C or so,
Then crosslinking sensitizer TMPTMA, anti-irradiation agent A high phenyl siloxane rubber (phenyl content 40%) and phenylene silicone rubber (penylene is added
Content is 60%), to be kneaded 5-10 minutes, be 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.
Application Example
By the high radiation resistance nuclear island inner cable halogen-free flameproof oversheath material of the extra long life of embodiment 1-7, by GB/
T12706.1-2008 cable production method, melting extrusion is coated at a temperature of 120-160 DEG C of single screw extrusion machine of φ 45-120
The double hyer insulation core wire and coated on halogen-free flameproof filled layer (oxygen barrier layer) cable that crosslinking with radiation has been crossed, jacket thickness is according to each
Kind cable specification requirement, crosslinking with radiation.The radiation source of the radiation is electron beam, the irradiation dose of the radiation
150-200KGy。
The high radiation resistance nuclear island inner cable halogen-free flameproof jacket material of extra long life of the invention and its cable of preparation
It can see the table below.
Table 1: the test method and standard of each test item:
Table 2: jacket material and cable performance
Table 2 (continuous 1)
By halogen-free flameproof oversheath material in the high radiation resistance nuclear island of the extra long life for preparing the embodiment of the present invention 1-7 and
Its nuclear power cable performance obtained is compared it can be concluded that following result:
(1) embodiment 1 and embodiment 2 are formulated, and formula components are consistent, and EVA increases 5kg in embodiment 2, reduces
EMMA5kg, 2 ageing properties of embodiment slightly reduce, other performances are consistent substantially, and it is resistance to show that addition EMMA can promote material
Ageing properties.
(2) embodiment 2 and embodiment 3 are formulated, in addition to embodiment 3 increases ethylene-octene copolymer (POE) in substrate
5kg reduces EVA5kg, other formulas are consistent, and the tensile strength of PERFORMANCE EXAMPLES 3, elongation at break conservation rate ratio are implemented
Example 2 slightly improves, and oxygen index (OI) is lower than embodiment 2, other performances are consistent substantially, obtains addition ethylene-octene copolymer
(POE) it is able to ascend the mechanical property of materials.
(3) embodiment 3 and embodiment 4 are formulated, and formula components are consistent, and hexaphenoxycyclotriphosphazene increases in embodiment 4
Add 3kg, and the nuclear power cable of the big specification of embodiment 3 can cannot pass through small dimension nuclear power cable by bunchy burning A/B class
Bunchy burning A/B class, embodiment 4 increases flame retardant hexaphenoxy cyclotriphosphazene dosage, fire-retardant to pass through size specification electricity
Cable, while radiation-resistant property also improves a lot, but cable smoke density also increases, and cannot pass through size specification cable smoke density mark
Standard increases material cost simultaneously because hexaphenoxycyclotriphosphazene is expensive.
The test of hexaphenoxycyclotriphosphazene Flouride-resistani acid phesphatase effect:
In air atmosphere, retention rate test is carried out using electron beam irradiation various dose (0-1000kGy).As a result table
Bright, hexaphenoxycyclotriphosphazene still retains 72.8% in 1000kGy, illustrates it with good anti-radiation ability.
(4) embodiment 4 and embodiment 5 are formulated, and formula components are consistent, and fumicants ammonium octamolybdate is sold in embodiment 5 than real
It applies example 4 and increases 0.5kg, 4 performance of embodiment is fire-retardant, radiation-resistant property can meet nuclear power cable standard, but smoke density is larger,
It is not able to satisfy various specifications cable, and 6 performance of embodiment can meet nuclear power cable all properties requirement, obtain eight molybdic acid of pin fumicants
Ammonium has preferable pin cigarette effect in the present invention.
(5) embodiment 5 and embodiment 6 are formulated, and are increased phenoxy group polyphosphazene 3kg in 6 fire retardant of embodiment, are reduced six
Phenoxy cyclotriphosphazene 3kg, other formula components are consistent, and 6 intensity of embodiment, to stretch rate, ageing properties and radiation-resistant property all low
In embodiment 5, flame retardant property is consistent, obtain phenoxy group polyphosphazene other than flame retardant effect is consistent with hexaphenoxycyclotriphosphazene,
Other performances are all low, but phenoxy group polyphosphazene price is far below hexaphenoxycyclotriphosphazene.
(6) embodiment 5 and embodiment 7 are formulated, and are increased phenoxy group polyphosphazene 1kg in 7 fire retardant of embodiment, are reduced six
Phenoxy cyclotriphosphazene 1kg, other formula components are consistent, and performance is substantially close with embodiment 5, obtain the poly- phosphorus of a small amount of phenoxy group
Nitrile, which substitutes hexaphenoxycyclotriphosphazene, influences less cable material, but can reduce material cost.
(7) embodiment 6 and embodiment 7 are formulated, and formula components are consistent, polyphosphazene flame retardant phenoxy group in embodiment 7
Polyphosphazene 1kg, hexaphenoxycyclotriphosphazene 7kg are respectively than reducing 2kg and increasing 2kg, polyphosphazene flame retardant total amount in embodiment 6
Constant, performance is close with embodiment 5, has larger improvement compared with 6 performance of embodiment, and obtaining cannot be replaced with a large amount of phenoxy group polyphosphazenes
For hexaphenoxycyclotriphosphazene.
Therefore by each in nuclear island inner cable halogen-free flameproof jacket material provided by the invention for can be seen that above
Component mutually cooperates with mutual restriction, and collective effect has reached the final beneficial effect of material of the present invention.
Claims (12)
1. a kind of nuclear island inner cable halogen-free flameproof jacket material, which is characterized in that raw material includes in parts by weight such as the following group
Point: 80-112 parts of polymeric substrate；80-100 parts of inorganic fire retardants；15-25 parts of zinc borate；8-12 parts of polyphosphazene flame retardant；Phosphorus
8-12 parts of nitrogenated flame retardant；1-3 parts of anti-aging agent；1-3 parts of smoke of gunpowder agent；4-8 parts of composite antioxidant；3-8 parts of anti-irradiation agent；Processing helps
6-12 parts of agent；
Wherein, the polymeric substrate includes the ethylene-vinyl acetate copolymer of radiation grafting maleic anhydride, ethylene-vinegar
In vinyl acetate copolymer, ethylene-octene copolymer or ethylene methyl methacrylate copolymer any one or a few
Combination.
2. nuclear island inner cable halogen-free flameproof jacket material according to claim 1, which is characterized in that the compound antioxygen
Agent includes primary antioxidant, auxiliary antioxidant and ultraviolet absorbing agent；Wherein, the primary antioxidant include pentaerythritol ester and/or
β-(3,5- di-tert-butyl -4- hydroxy phenyl) propionic acid octadecyl ester；The auxiliary antioxidant includes sulphur ester antioxidant；It is described ultraviolet
Light absorbers include 2- (bis- tertiary amyl phenyl of 2'- hydroxyl -3', 5'-) benzotriazole, 2- (2'- hydroxyl -5'- spy octyl phenyl)
One or more of benzotriazole or 2- (bis- (a, a- dimethyl benzyl) phenyl of 2'- hydroxyl -3', 5'-) benzotriazole.
3. nuclear island inner cable halogen-free flameproof jacket 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.
4. nuclear island inner cable halogen-free flameproof jacket material according to claim 3, which is characterized in that the processing aid
Including crosslinking sensitizer and lubricant.
5. nuclear island inner cable halogen-free flameproof jacket material according to claim 4, 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-
The combination of one or more of ethylene waxes, zinc stearate and calcium stearate.
6. nuclear island inner cable halogen-free flameproof jacket material according to claim 1, which is characterized in that the polymer matrix
Material is that ethylene-vinyl acetate copolymer, ethylene-vinyl acetate copolymer, the ethylene-octene of radiation grafting maleic anhydride are total
Polymers and ethylene methyl methacrylate copolymer, wherein the ethylene-vinyl acetate copolymer of radiation grafting maleic anhydride,
Ethylene-vinyl acetate copolymer, ethylene-octene copolymer and ethylene methyl methacrylate copolymer weight fraction ratio are
5-15:10-30:5-15:60-80。
7. nuclear island inner cable halogen-free flameproof jacket material according to claim 2, which is characterized in that the main antioxygen
The ratio of the addition quality of agent, auxiliary antioxidant and ultraviolet absorbing agent is 1:1-3:0.1-0.7.
8. nuclear island inner cable halogen-free flameproof jacket material according to claim 3, which is characterized in that anti-irradiation agent A and
The mass ratio of anti-irradiation agent B is 3-4:1-2.
9. the preparation method of nuclear island inner cable halogen-free flameproof jacket material as claimed in claim 4, which is characterized in that will polymerize
Object substrate, inorganic fire retardants, zinc borate, polyphosphazene flame retardant, phosphorus-nitrogen containing flame retardant, anti-aging agent, composite antioxidant, anti-irradiation agent
B, lubricant and environment-friendly type Masterbatch are put into mixer and are kneaded, and are kneaded 5 minutes after melting to 130 DEG C or so, are then added and hand over
Join sensitizer and anti-irradiation agent A, be kneaded 5-10 minutes in 130-150 DEG C of temperature range, is then lifted out to double rank twin-screws and squeezes
Machine out, the air-cooled extruding pelletization in 120-160 DEG C of temperature range.
10. a kind of nuclear island inner cable halogen-free flameproof external sheath layer, which is characterized in that its raw material includes any one of claim 1-8
The nuclear island inner cable halogen-free flameproof jacket material.
11. the preparation method of nuclear island inner cable halogen-free flameproof external sheath layer described in any one of claim 10, which is characterized in that by nuclear island
By single screw extrusion machine, melting extrusion under the conditions of 120-160 DEG C is coated on and has radiated inner cable halogen-free flameproof jacket material
It the double hyer insulation core wire that was crosslinked and has coated on halogen-free flameproof filled layer cable, crosslinking with radiation.
12. the preparation method of nuclear island inner cable halogen-free flameproof external sheath layer according to claim 11, which is characterized in that institute
The radiation source for stating crosslinking with radiation is electron beam, the irradiation dose 150-200KGy of the radiation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811299995.0A CN109575409A (en) | 2018-11-02 | 2018-11-02 | Nuclear island inner cable halogen-free flameproof jacket material, cable jacket layer and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811299995.0A CN109575409A (en) | 2018-11-02 | 2018-11-02 | Nuclear island inner cable halogen-free flameproof jacket material, cable jacket layer and preparation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109575409A true CN109575409A (en) | 2019-04-05 |
Family
ID=65921454
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811299995.0A Pending CN109575409A (en) | 2018-11-02 | 2018-11-02 | Nuclear island inner cable halogen-free flameproof jacket material, cable jacket layer and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109575409A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112175278A (en) * | 2020-10-16 | 2021-01-05 | 青岛汉缆股份有限公司 | Thermoplastic halogen-free flame-retardant polyolefin sheath material for ultrahigh-voltage cable and preparation method and application thereof |
| CN112225982A (en) * | 2020-10-16 | 2021-01-15 | 常州八益电缆股份有限公司 | Rod position reactor top signal cable for nuclear power station |
| CN112225983A (en) * | 2020-10-16 | 2021-01-15 | 常州八益电缆股份有限公司 | Flame-retardant sheath material for nuclear power station cable, preparation method and service life detection method |
| CN115785576A (en) * | 2022-12-06 | 2023-03-14 | 合肥工业大学 | Gamma-ray irradiation resistant ceramic flame-retardant fire-resistant cable sheath material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070149680A1 (en) * | 2003-11-12 | 2007-06-28 | Kim Oh Y | Halogen free polymer and automotive wire using thereof |
| CN102875947A (en) * | 2012-09-20 | 2013-01-16 | 中国科学院上海应用物理研究所 | Halogen-free flame retardant sheath material for nuclear cable, cable sheath, preparation method and application |
| CN207993540U (en) * | 2018-02-08 | 2018-10-19 | 京缆电缆有限公司 | A kind of fireproof cable |
-
2018
- 2018-11-02 CN CN201811299995.0A patent/CN109575409A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070149680A1 (en) * | 2003-11-12 | 2007-06-28 | Kim Oh Y | Halogen free polymer and automotive wire using thereof |
| CN102875947A (en) * | 2012-09-20 | 2013-01-16 | 中国科学院上海应用物理研究所 | Halogen-free flame retardant sheath material for nuclear cable, cable sheath, preparation method and application |
| CN207993540U (en) * | 2018-02-08 | 2018-10-19 | 京缆电缆有限公司 | A kind of fireproof cable |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112175278A (en) * | 2020-10-16 | 2021-01-05 | 青岛汉缆股份有限公司 | Thermoplastic halogen-free flame-retardant polyolefin sheath material for ultrahigh-voltage cable and preparation method and application thereof |
| CN112225982A (en) * | 2020-10-16 | 2021-01-15 | 常州八益电缆股份有限公司 | Rod position reactor top signal cable for nuclear power station |
| CN112225983A (en) * | 2020-10-16 | 2021-01-15 | 常州八益电缆股份有限公司 | Flame-retardant sheath material for nuclear power station cable, preparation method and service life detection method |
| CN115785576A (en) * | 2022-12-06 | 2023-03-14 | 合肥工业大学 | Gamma-ray irradiation resistant ceramic flame-retardant fire-resistant cable sheath material and preparation method thereof |
| CN115785576B (en) * | 2022-12-06 | 2024-04-05 | 合肥工业大学 | Gamma-ray radiation resistant ceramic flame-retardant fire-resistant cable sheath material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109575409A (en) | Nuclear island inner cable halogen-free flameproof jacket material, cable jacket layer and preparation method | |
| CN102875947B (en) | Halogen-free flame retardant sheath material for nuclear cable, cable sheath, preparation method and application | |
| CN102952316B (en) | Halogen-free inflaming retarding insulating material of nuclear cable and cable insulating layer as well as preparation method and application thereof | |
| CN102093625B (en) | Low smoke non-halogen one-stage process silane naturally crosslinked polyolefin cable material and preparation method thereof | |
| CN109575418A (en) | 105 DEG C of oil-resisting type irradiated crosslinking low-smoke and halogen-free flame retardant CABLE MATERIALSs and preparation method thereof | |
| CN103087377B (en) | A kind of nuclear power 1 E-level K 3-type heat-shrinkable T bush material and preparation thereof | |
| CN104650446A (en) | Nano-clay-containing irradiation crosslinked polyolefin cable material and preparation method thereof | |
| CN104403190A (en) | Ultraviolet cross-linking oil-resistant low-smoke halogen-free flame retardant polyolefin cable material and preparation method thereof | |
| CN101914236A (en) | Irradiation crosslinking halogen-free high flame-retardant cable material and preparation method thereof | |
| WO2021129217A1 (en) | Low-smoke and halogen-free building wire and cable material, and preparation method therefor | |
| CN100999598A (en) | Preparation process for cable material of radiation resisting low flue unhalogen flame-retarded ethylpropyl rubber | |
| CN101456991B (en) | Halogen-free flame retardant sheath material | |
| CN102485782A (en) | Crosslinked, oil-resistant, low temperature-resistant, low-smoke, halogen-free and flame-retardant cable material and its preparation method | |
| CN105860247A (en) | Low-smoke halogen-free building cable insulation material and preparation method thereof | |
| CN111004433A (en) | Irradiation crosslinking low-smoke halogen-free sheath material for photovoltaic cable and preparation method thereof | |
| CN101880417A (en) | Silane crosslinked halogen-free flame-retardant polyethylene cable material and preparation method thereof | |
| SA112330583B1 (en) | Eco friendly crosslinked flame retardant composition for wire and cable | |
| CN109957199A (en) | A kind of photovoltaic cable smoke halogen-free flame retardant sheath material and its preparation method and application | |
| CN110041607A (en) | A kind of metal hydroxides-boron nitride hydridization filler/blend rubber nuclear power cable Insulation Material and preparation method | |
| CN103554639B (en) | A kind of production method of environment-friendly halogen-free flame-proof electric wire | |
| CN103589076A (en) | Radiation-resistant halogen-free flame-retardant cable material and preparation method thereof | |
| CN102731894B (en) | High temperature resistant anti-cracking high-flame retarding irradiation crosslinking low smoke zero halogen cable material and preparation method | |
| CN102604196A (en) | Cable jacket material for nuclear power station of third generation and preparation method for cable jacket material | |
| CN102492197A (en) | Sheath material for photovoltaic cable | |
| CN109593260A (en) | Halogen-free flame-retardant thermal shrinkage material in a kind of nuclear island, halogen-free flameproof heat-shrinkable tube and preparation method thereof in nuclear island |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190405 |
|
| RJ01 | Rejection of invention patent application after publication |