CN102875947B - Halogen-free flame retardant sheath material for nuclear cable, cable sheath, preparation method and application - Google Patents
Halogen-free flame retardant sheath material for nuclear cable, cable sheath, preparation method and application Download PDFInfo
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Abstract
The invention discloses a halogen-free flame retardant sheath material for a nuclear cable, a cable sheath, and a preparation method and an application of the cable sheath. The halogen-free flame retardant sheath material for the nuclear cable comprises the following raw materials: 100 parts of a polymer base material comprising ethylene vinyl acetate copolymer and ethylene methyl methacrylate copolymer, 100-140 parts of an inorganic fire retardant comprising magnesium oxide, 15-25 parts of phenoxycycloposphazene; 15-30 parts of nitrogen fire retardant comprising melamine cyanurate, 4-8 parts of a compound antioxidant comprising a main antioxidant, an auxiliary antioxidant and an ultraviolet light absorber, 5-15 parts of an anti-radiation agent comprising high phenyl siloxane rubber and an anti-radiation agent A, and 6-12 parts of a processing aid comprising a cross-linking sensitizing agent and a lubricant, wherein the anti-radiation agent A is boron carbide and/or boron nitride. The halogen-free sheath material for the nuclear cable disclosed by the invention is good in superior performance, good fire retardant performance, and stable anti-radiation performance, electrical performance and mechanical performance.
Description
Technical field
The present invention relates to cable halogen-free flameproof sheath material, cable sheath for a kind of core, and its preparation method and application.
Background technology
Generation Ⅲ nuclear power, as the U.S. AP1000 of Xi Wo company nuclear power generating sets, Yi China builds in a large number.For the overall situation and the long term growth of China's science and technology, it is special that the Chinese Academy of Sciences proposes strategic guide's science and technology, following advanced nuclear fission energy (the 4th generation)---the development work of thorium base MSR nuclear power system (TMSR).No matter be the third generation or the 4th generation of technology such as nuclear energy system, the insulation of the cable of nuclear power and cable accessory and sheath material must have good long term heat ageing performance, and (at first and second 90 ℃ of nuclear power generating sets, Long Service Life is 40 years in generation, at third and fourth 90 ℃ of nuclear power generating sets, Long Service Life is 60 years in generation), the feature such as stable radiation-resistant property and electric property, good flame retardant properties and low cigarette, Halogen, low toxicity.
The sill of conventional cable for nuclear power station sheath material adopts vinyl-vinyl acetate copolymer (EVA) material, the vinyl-acetic ester-CH in EVA material conventionally
2cHCOOCH
3-under long term heat ageing effect and under a large amount of radiation exposure, produce living radical (COO-) or active ion, and can further there is chemical reaction, living radical or active ion cause DeR, crosslinking reaction, oxidizing reaction and the molecule isomerization reaction of macromolecular chain, these reactions make material molecule reaction rate accelerates, and sheath material can become fragile, mechanical property variation, particularly the elongation at break of material declines to a great extent, and affects materials'use.
In addition, as the vinyl-vinyl acetate copolymer of polymeric substrate, be inflammable macromolecular material, in order to make sheath material reach cable category-A bunchy vertical combustion, must add a large amount of halogen-free flame retardantss.General halogen-free flame retardants will reach this flame retardant properties, and its addition must be greater than 50%.After the so many fire retardant of general Material Addition, mechanical property all can not meet the basic demand of nuclear power K1 sheath material, in order to improve the most effective way of mechanical property of material, in polymeric substrate, add Its Compatibilizing Technology exactly, conventionally adopt in the market the ethylene-vinyl acetate copolymer (EVA-g-MAH) of chemical graft maleic anhydride functional group as compatilizer (percentage of grafting is 0.8-1%).
Patent CN101456992A adopts the compounded technology of single inorganic combustion inhibitor, total institute is known, adopt the single inorganic combustion inhibitor fire retardant material oxygen index numerical value can very high (oxygen index is 37.6), but differ surely by the single testing vertical flammability of nuclear power cable insulation layer.The resistance to irradiation test of this patent is 550KGy simultaneously, and 1500KGy radiation-resistant property of the present invention requirement is far from.
Adopt single composite inorganic combustion inhibitor will meet cable-flame retardant standard, single vertical combustion standard, certainly will need to add a large amount of inorganic combustion inhibitors, affects sheath material mechanical property, and this problem is also urgently to be resolved hurrily.
Summary of the invention
Technical problem to be solved by this invention is to overcome the defect of the problems such as existing cables of nuclear power sheath material long term heat ageing, halogen-free flameproof performance are not ideal enough, bad mechanical property, the preparation method and application of cable halogen-free flameproof sheath material, cable sheath for a kind of core are provided, sheath material superior performance of the present invention, there is good flame retardant properties, stable radiation-resistant property, electric property and mechanical property.
One of technical scheme of the present invention is that the preparation method of a kind of core with cable halogen-free flameproof sheath material is provided;
It comprises the raw material of following weight part:
Polymeric substrate: 100 parts; Inorganic combustion inhibitor: 100-140 part; Polyphosphonitrile fire retardant: 15-25 part; Nitrogenated flame retardant: 15-30; Composite antioxidant: 4-8 part; Anti-irradiation agent: 5-15 part; Processing aid: 6-12 part;
Wherein said polymeric substrate comprises compatilizer and ethylene-methyl methacrylate methyl terpolymer (EMMA); Wherein, described compatilizer is the ethylene-vinyl acetate copolymer (EVA-g-MAH) of radiation grafting maleic anhydride;
Described inorganic combustion inhibitor comprises magnesium hydroxide;
Described polyphosphonitrile fire retardant comprises hexaphenoxycyclotriphosphazene;
Described nitrogenated flame retardant comprises melamine cyanurate (MCA);
Described composite antioxidant comprises primary antioxidant, auxiliary antioxidant and UV light absorber;
Wherein, described primary antioxidant comprises pentaerythritol ester (antioxidant 1010) and/or β-(3,5-di-tert-butyl-4-hydroxy phenyl) propionic acid octadecyl ester (antioxidant 1076);
Described auxiliary antioxidant comprises sulphur ester antioxidant;
Described UV light absorber comprises 2-(2'-hydroxyl-3', 5'-bis-tertiary amyl phenyl) one or more in benzotriazole (UV-328), 2-(the special octyl phenyl of 2'-hydroxyl-5'-) benzotriazole (UV-329) and 2-(2'-hydroxyl-3', two (a, the a-dimethyl benzyl) phenyl of 5'-) benzotriazole (UV-234);
Described anti-irradiation agent comprises anti-irradiation agent A and anti-irradiation agent B, and wherein anti-irradiation agent A is high phenyl siloxane rubber and/or phenylene silicone rubber; Anti-irradiation agent B is norbide and/or boron nitride;
Described processing aid comprises crosslinking sensitizer and lubricant;
Wherein said crosslinking sensitizer comprises trimethylolpropane trimethacrylate (TMPTMA) and/or iso-cyanuric acid triallyl ester (TAIC), and described lubricant comprises one or more in polyethylene wax, Zinic stearas and calcium stearate.
Preferably, core of the present invention with raw material and the weight part thereof of cable halogen-free flameproof sheath material is: polymeric substrate: 100 parts; Inorganic combustion inhibitor: 100-140 part; Polyphosphonitrile fire retardant: 15-25 part; Nitrogenated flame retardant: 15-30; Composite antioxidant: 4-8 part; Anti-irradiation agent: 5-15 part; Processing aid: 6-12 part;
Wherein, the composition of above-mentioned substance and content are as previously mentioned.
The polymkeric substance of cable halogen-free flameproof sheath material for core of the present invention: the ratio of the parts by weight of halogen-free flame retardants reaches 1:1.5 left and right, be that halogen-free flame retardants addition accounts for 60% left and right, in order to improve the mechanical property of material, sheath material of the present invention adopts to have knows the ethylene-vinyl acetate copolymer with maleic anhydride functional group (EVA-g-MAH) prepared by intellecture property (ZL20061002875.5) radiation grafting technology as compatilizer (percentage of grafting >=1%), this compatilizer has higher percentage of grafting, make polymeric substrate and halogen-free flame retardants have better consistency, than the sheath material that adds chemical compatibility agent, there is better mechanical property.
In the present invention, preferably, the preparation method of the ethylene-vinyl acetate copolymer of described radiation grafting maleic anhydride can be with reference to Chinese patent ZL200610028750.5;
Better, the preparation method of the ethylene-vinyl acetate copolymer of described radiation grafting maleic anhydride is: the maleic anhydride of 1 ~ 5 part is dissolved in acetone, mix with 100 parts of ethylene-vinyl acetate copolymers, Deng granulation in twin screw extruder after acetone volatilization, at rumbatron electron rays or gamma-rays, carry out radiation again, radiation dose is 5 ~ 30KGy.
In the present invention, preferably, described ethylene-methyl methacrylate methyl terpolymer (EMMA) is block copolymerization; The ratio of weight and number of described compatilizer and ethylene-methyl methacrylate methyl terpolymer (EMMA) is (5-15): (85-95).
In the present invention, preferably, in ethylene-methyl methacrylate methyl terpolymer (EMMA), polymer unit methyl methacrylate (MMA) accounts for the molar percentage 14%-40% of total polymer unit in multipolymer; Better, the melting index MI of ethylene-methyl methacrylate methyl terpolymer (EMMA) is 2-6;
In the present invention, preferably, described polymeric substrate also comprises ethylene-vinyl acetate copolymer (EVA); When containing ethylene-vinyl acetate copolymer (EVA), and when compatilizer is the ethylene-vinyl acetate copolymer (EVA-g-MAH) of radiation grafting maleic anhydride, described ethylene-methyl methacrylate methyl terpolymer (EMMA): the ratio of weight and number of ethylene-vinyl acetate copolymer (EVA) is (70-95): (5-30).
In the present invention, preferably described ethylene-methyl methacrylate methyl terpolymer (EMMA) and ethylene-vinyl acetate copolymer (EVA) is block copolymerization;
In the present invention, preferably, in ethylene-vinyl acetate copolymer (EVA), polymer unit vinyl acetate (VA) accounts for the molar percentage 14%-40% of total polymer unit in multipolymer; Better, the melting index MI of ethylene-vinyl acetate copolymer (EVA) is 2-6.
In the present invention, preferably, described inorganic combustion inhibitor can also comprise aluminium hydroxide and/or zinc borate; Preferably, when adding aluminium hydroxide, described magnesium hydroxide and the ratio of weight and number of aluminium hydroxide are (60-90): (40-10); When adding zinc borate, described magnesium hydroxide and the ratio of weight and number of zinc borate are (70-95): (30-5); When adding aluminium hydroxide and zinc borate, the ratio of weight and number of the addition of described magnesium hydroxide, aluminium hydroxide and zinc borate is (50-100): (5-50): (5-30) simultaneously.
In the present invention, preferably, the preparation method of described hexaphenoxycyclotriphosphazene can reference:
1, Halogen efficient flame-retarding agent HPCTP's is synthetic, and Yang Xin changes etc., representation and application research-phenetic analysis, and China is fire-retardant; 2011,3:11-12;
2, Tang Anbin etc., applied chemistry, 2010.07,27 (4): 404-408;
3, Kong Xiang builds etc., plastics industry, 2011.07,39 (7): 68-71;
Better, the synthetic method of described hexaphenoxycyclotriphosphazene is:
1), the preparation of phenol sodium salt: the sodium hydroxide solution (wherein the amount of sodium hydroxide is 2.0mol) that adds 2kg phenol, 10L chlorobenzene, 200g polyoxyethylene glycol, 45% (weight percent) under nitrogen protection; 120 ~ 130 ℃ of temperature of reaction; 8 ~ 12 hours reaction times; after completion of the reaction; carry out component distillation and divide after water outlet, it is stand-by that reactant is cooled to room temperature.
2) in the phenol sodium salt of preparing, the preparation of hexaphenoxycyclotriphosphazene: in step 1); under nitrogen protection, add 30% chlorobenzene solution that contains 1.16kg hexachlorocyclotriphosphazene; under 130 ~ 132 ℃ of conditions, react 6 ~ 12 hours, cooling, filter; filtrate decompression distillation; reclaim solvent chlorobenzene, in resultant product, add hot ethanol, washing; suction filtration is dried to obtain hexaphenoxycyclotriphosphazene 2.04kg, productive rate 88%.
In the present invention, preferably, described sulphur ester antioxidant is the two octadecyl esters (oxidation inhibitor DSTP) of Tyox B (anti-oxidant DLTP) and/or thio-2 acid.
In the present invention, preferably, described UV light absorber is 2-(2'-hydroxyl-3', 5'-bis-tertiary amyl phenyl) benzotriazole (UV-328).
In the present invention preferably, described primary antioxidant: auxiliary antioxidant: the weight fraction of the addition of UV light absorber is than being 1:(1-3): (0.1-0.5).
In the present invention, preferably, the parts by weight of described crosslinking sensitizer are 1-3 part, and the parts by weight of described lubricant are 2-5 part.
In the present invention, preferably, described processing aid also comprises carbon black; The parts by weight of described carbon black are 2-4 part.
Preferably, the preparation method of halogen-free flameproof sheath material of the present invention is: according to aforementioned proportion, polymeric substrate, inorganic combustion inhibitor, polyphosphonitrile fire retardant, nitrogenated flame retardant, composite antioxidant and anti-irradiation agent B are put into Banbury mixer mixing, after melting, add processing aid and anti-irradiation agent A, in 120 ~ 140 ℃ of temperature ranges mixing 10 ~ 20 minutes, after be promoted to twin screw extruder air-cooled extruding pelletization in 110 ~ 150 ℃ of temperature ranges;
While containing carbon black in raw material, its step comprises: according to the above ratio polymeric substrate, inorganic combustion inhibitor, polyphosphonitrile fire retardant, nitrogenated flame retardant, composite antioxidant, anti-irradiation agent B and carbon black are put into Banbury mixer mixing, after melting, add crosslinking sensitizer, lubricant and anti-irradiation agent A, in 120 ~ 140 ℃ of temperature ranges mixing 10 ~ 20 minutes, after be promoted to twin screw extruder air-cooled extruding pelletization in 110 ~ 150 ℃ of temperature ranges.
In the present invention, purchase producer and the model of above-mentioned raw materials are respectively:
Ethylene-methyl methacrylate methyl terpolymer (EMMA): SUMITOMO CHEMICAL company, du pont company;
Ethylene-vinyl acetate copolymer (EVA): Beijing Organic Chemical Plant, French Arkema, du pont company;
Melamine cyanurate (MCA): the gloomy halogen-free smoke resistance flame resistance agent of Shanghai rising sun company limited;
High phenyl siloxane rubber: Jiangsu Hongda new materials Co., Ltd;
Crosslinking sensitizer TMPTMA: Nanjing is science and trade limited liability company hand in hand;
Crosslinking sensitizer TAIC: Shanghai addition Chemical Co., Ltd..
Two of technical scheme of the present invention is that the core that aforesaid method makes cable halogen-free flameproof sheath material is provided.
Three of technical scheme of the present invention is to provide the core that aforesaid method makes preparing the application of core with K1 class halogen-free flameproof power cable restrictive coating with cable halogen-free flameproof sheath material.
Preferably, the insulated cable layer that halogen-free flameproof sheath material of the present invention can be prepared with cable halogen-free flame retardant insulation material for the preparation of the employing core that is coated on three cores.Four of technical scheme of the present invention is that the preparation method of above-mentioned core with K1 class halogen-free flameproof power cable restrictive coating is provided.The method is: core of the present invention extruded with cable halogen-free flameproof sheath material, is coated on inner core, and radiation crosslinking.
Preferably, the source of radiation of described radiation is electron beam, and the irradiation dose of described radiation is 120-180Kgy.
Concrete preparation method can reference: GB/T12706.1-2008.
Five of technical scheme of the present invention is that the K1 class halogen-free flameproof power cable restrictive coating for core being made by the method described in technique scheme four is provided.
Meeting on the basis of this area general knowledge, above-mentioned each optimum condition, can arbitrary combination, obtains the preferred embodiments of the invention.
Agents useful for same of the present invention and raw material be commercially available obtaining all.
Positive progressive effect of the present invention is: the core that the present invention makes protects material superior performance with cable halogen-free flameproof, has good flame retardant properties, stable radiation-resistant property, electric property and mechanical property.The process 1-10KGy/h of power cable prepared by sheath material of the present invention, integral dose 1500KGy
60after Cov-radiation exposure, the elongation at break of material remains on more than 50%, more than radiation hardness dosage can reach 1500KGy simultaneously, through the cable of thermal ageing and radiation aging, can test by LOCK.Electrical property meets IEEE383-2003 standard related request, sheath material of the present invention has added the anti-irradiation agent such as boron nitride, high phenyl siloxane rubber in polymeric substrate, effectively suppress the destruction of ν-ray under nuclear environment, reduce the splitting of chain that the intermolecular C-C key of polymer materials causes because being stimulated, extended material work-ing life under nuclear environment.In material prescription, introduce high efficiency composition oxidation inhibitor, intercepted free radical and generated new free radical as intermediate and polymkeric substance simultaneously, thus control degradation speed, and through the reckoning of Arrhenius equation, material can be used more than 60 years at 90 ℃ of temperature.
Embodiment
Mode below by embodiment further illustrates the present invention, but does not therefore limit the present invention among described scope of embodiments.The experimental technique of unreceipted actual conditions in the following example, according to ordinary method and condition, or selects according to catalogue.
In embodiments of the invention, purchase producer and the model of described raw material are as follows:
Oxidation inhibitor, ultraviolet absorbers: Ciba (China) company limited, Milan, Nanjing Chemical Co., Ltd.;
Boron nitride: Yingkou Liao Bin Fine Chemical Co., Ltd;
Norbide: Mudanjiang professional production norbide company limited;
Polyethylene wax: Shanghai Xin Lan Chemical Co., Ltd.
Magnesium hydroxide: Dalian Ya Tai Science and Technology Co., Ltd.;
Aluminium hydroxide: Shandong Aluminium Industry Co., Ltd;
Zinc borate: the gloomy halogen-free smoke resistance flame resistance agent of Shanghai rising sun company limited.
Embodiment 1
Synthesizing of polyphosphonitrile flame retardant hexaphenoxy cyclotriphosphazene:
Concrete operations technique is:
1), the preparation of phenol sodium salt: in the stainless steel cauldron of 100L; under nitrogen protection, add 10Kg phenol, 50L chlorobenzene, 1Kg polyoxyethylene glycol, 45% sodium hydroxide solution; the sodium hydroxide that wherein contains 10mol; temperature of reaction 120-130 ℃; reaction times 8-12 hour; after completion of the reaction, carry out component distillation and divide after water outlet, it is stand-by that reactant is cooled to room temperature.
2) in the phenol sodium salt of, the preparation of hexaphenoxycyclotriphosphazene: in step 1) preparing; 30% chlorobenzene solution that adds the hexachlorocyclotriphosphazene that contains commercial 5.8Kg under nitrogen protection; at 130-132 ℃ of temperature, react 6-12 hour, cooling, filter; filtrate is carried out to underpressure distillation; reclaim solvent chlorobenzene, in resultant product, add hot ethanol, washing; suction filtration is dried to obtain hexaphenoxycyclotriphosphazene 9.6Kg, productive rate 82.8%.
Embodiment 2
Raw material:
Wherein, polyphosphonitrile fire retardant used is the hexaphenoxycyclotriphosphazene making in embodiment 1.
Operation steps:
By compatilizer EVA-g-MAH, ethylene-methyl methacrylate methyl terpolymer, (EMMA, antioxidant 1010, anti-oxidant DLTP, ultraviolet (UV) 328, boron nitride, magnesium hydroxide, melamine cyanurate (MCA), hexaphenoxycyclotriphosphazene and carbon black are put into 35 liters of Banbury mixeies, during banburying to 130 ℃, add high phenyl siloxane rubber (phenyl content 40%, Zinic stearas, triallyl isocyanurate (TAIC), after mixing 10 minutes, (banburying temperature 120-140 ℃) turnover internal mixer, pours material in lift into and is promoted to
twin screw extruder, at 110-150 ℃ of extruding pelletization, air-cooled, obtain nuclear power K1 halogen-free flameproof sheath material.
Embodiment 3
Raw material:
Wherein, polyphosphonitrile fire retardant used is the hexaphenoxycyclotriphosphazene making in embodiment 1.
Operation steps:
Compatilizer EVA-g-MAH, ethylene-methyl methacrylate methyl terpolymer (EMMA), ethylene-vinyl acetate copolymer (EVA), antioxidant 1010, anti-oxidant DLTP, ultraviolet (UV) 328, boron nitride, magnesium hydroxide, melamine cyanurate (MCA), hexaphenoxycyclotriphosphazene and carbon black are put into 35 liters of Banbury mixeies, during banburying to 130 ℃, add high phenyl siloxane rubber (phenyl content 40%, Zinic stearas, triallyl isocyanurate (TAIC), after mixing 10 minutes, (banburying temperature 120-140 ℃) turnover internal mixer, pours material in lift into and is promoted to
twin screw extruder, at 110-150 ℃ of extruding pelletization, air-cooled, obtain nuclear power K1 halogen-free flameproof sheath material.
Embodiment 4
Raw material:
Wherein, polyphosphonitrile fire retardant used is the hexaphenoxycyclotriphosphazene making in embodiment 1.
Operation steps:
Compatilizer EVA-g-MAH, ethylene-methyl methacrylate methyl terpolymer (EMMA), antioxidant 1010, anti-oxidant DLTP, ultraviolet (UV) 328, boron nitride, magnesium hydroxide, melamine cyanurate (MCA), hexaphenoxycyclotriphosphazene and carbon black are put into 35 liters of Banbury mixeies, during banburying to 130 ℃, add high phenyl siloxane rubber (phenyl content 40%, Zinic stearas, calcium stearate, triallyl isocyanurate (TAIC), after mixing 10 minutes, (banburying temperature 120-140 ℃) turnover internal mixer, pours material in lift into and is promoted to
twin screw extruder, at 110-150 ℃ of extruding pelletization, air-cooled, obtain nuclear power K1 halogen-free flameproof sheath material.
Embodiment 5
Raw material:
Wherein, polyphosphonitrile fire retardant used is the hexaphenoxycyclotriphosphazene making in embodiment 1.
Operation steps:
Compatilizer EVA-g-MAH, ethylene-methyl methacrylate methyl terpolymer (EMMA), ethylene-vinyl acetate copolymer (EVA), antioxidant 1076, oxidation inhibitor DSTP, ultraviolet (UV) 329, boron nitride, magnesium hydroxide, aluminium hydroxide, zinc borate, melamine cyanurate (MCA), hexaphenoxycyclotriphosphazene and carbon black are put into 35 liters of Banbury mixeies, during banburying to 130 ℃, add high phenyl siloxane rubber (phenyl content 40%), polyethylene wax to refine (banburying temperature 120-140 ℃) turnover internal mixer after 10 minutes, material is poured in lift and is promoted to
twin screw extruder, at 110-150 ℃ of extruding pelletization, air-cooled, obtain nuclear power K1 halogen-free flameproof sheath material.
Embodiment 6
Raw material:
Wherein, polyphosphonitrile fire retardant used is the hexaphenoxycyclotriphosphazene making in embodiment 1.
Operation steps:
By compatilizer EVA-g-MAH, ethylene-methyl methacrylate methyl terpolymer (EMMA), ethylene-vinyl acetate copolymer (EVA), antioxidant 1076, anti-oxidant DLTP, ultraviolet (UV) 329, norbide, magnesium hydroxide, aluminium hydroxide, zinc borate, melamine cyanurate (MCA), hexaphenoxycyclotriphosphazene and carbon black are put into 35 liters of Banbury mixeies, during banburying to 130 ℃, add high phenyl siloxane rubber (phenyl content 40%), polyethylene wax, trimethylolpropane trimethacrylate (TMPTMA) is (banburying temperature 120-140 ℃) turnover internal mixer after mixing 10 minutes, material is poured in lift and is promoted to
twin screw extruder, at 110-150 ℃ of extruding pelletization, air-cooled, obtain nuclear power K1 halogen-free flameproof sheath material.
Embodiment 7
Raw material:
Wherein, polyphosphonitrile fire retardant used is the hexaphenoxycyclotriphosphazene making in embodiment 1.
Operation steps:
By compatilizer EVA-g-MAH, ethylene-methyl methacrylate methyl terpolymer (EMMA), ethylene-vinyl acetate copolymer (EVA), antioxidant 1010, anti-oxidant DLTP, ultraviolet (UV) 328, boron nitride, magnesium hydroxide, aluminium hydroxide, zinc borate, melamine cyanurate (MCA), hexaphenoxycyclotriphosphazene and carbon black are put into 35 liters of Banbury mixeies, during banburying to 130 ℃, add high phenyl siloxane rubber (phenyl content 40%), Zinic stearas, triallyl isocyanurate (TAIC) is (banburying temperature 120-140 ℃) turnover internal mixer after mixing 10 minutes, material is poured in lift and is promoted to
twin screw extruder, at 110-150 ℃ of extruding pelletization, air-cooled, obtain nuclear power K1 halogen-free flameproof sheath material.
Embodiment 8
Raw material:
Wherein, polyphosphonitrile fire retardant used is the hexaphenoxycyclotriphosphazene making in embodiment 1.
Operation steps:
By compatilizer EVA-g-MAH, ethylene-methyl methacrylate methyl terpolymer (EMMA), ethylene-vinyl acetate copolymer (EVA), antioxidant 1010, anti-oxidant DLTP, ultraviolet (UV) 328, boron nitride, magnesium hydroxide, aluminium hydroxide, zinc borate, melamine cyanurate (MCA), hexaphenoxycyclotriphosphazene and carbon black are put into 35 liters of Banbury mixeies, during banburying to 130 ℃, add high phenyl siloxane rubber (phenyl content 40%), Zinic stearas, triallyl isocyanurate (TAIC) is (banburying temperature 120-140 ℃) turnover internal mixer after mixing 10 minutes, material is poured in lift and is promoted to
twin screw extruder, at 110-150 ℃ of extruding pelletization, air-cooled, obtain nuclear power K1 halogen-free flameproof sheath material.
Embodiment 9
Raw material:
Wherein, polyphosphonitrile fire retardant used is the hexaphenoxycyclotriphosphazene making in embodiment 1.
Operation steps:
By compatilizer EVA-g-MAH, ethylene-methyl methacrylate methyl terpolymer (EMMA), ethylene-vinyl acetate copolymer (EVA), antioxidant 1010, anti-oxidant DLTP, ultraviolet (UV) 234, boron nitride, norbide, magnesium hydroxide, aluminium hydroxide, zinc borate, melamine cyanurate (MCA), hexaphenoxycyclotriphosphazene and carbon black are put into 35 liters of Banbury mixeies, during banburying to 130 ℃, add high phenyl siloxane rubber (phenyl content 40%), Zinic stearas, triallyl isocyanurate (TAIC) is (banburying temperature 120-140 ℃) turnover internal mixer after mixing 10 minutes, material is poured in lift and is promoted to
twin screw extruder, at 110-150 ℃ of extruding pelletization, air-cooled, obtain nuclear power K1 halogen-free flameproof sheath material.
Embodiment 10
Anti-irradiation agent in raw material, replaces high phenyl siloxane rubber with phenylene silicone rubber, and all the other raw materials and processing step are with embodiment 2.
Embodiment 11
Anti-irradiation agent in raw material, replaces high phenyl siloxane rubber with phenylene silicone rubber, and all the other raw materials and processing step are with embodiment 3.
Embodiment 12
Anti-irradiation agent in raw material, replaces high phenyl siloxane rubber with phenylene silicone rubber, and all the other raw materials and processing step are with embodiment 4.
Application Example
Nuclear power K1 halogen-free flameproof sheath material by embodiment 2-9 is extruded by single screw extrusion machine group, be coated on the insulated cable layer that the employing core of three cores is prepared with cable halogen-free flame retardant insulation material, by rumbatron radiation crosslinking, dosage 120-180KGy, prepares nuclear power K1 halogen-free flameproof restrictive coating.
Table 1: the test method of each test event is and standard is:
Table 2: sheath material and cable performance
By thorium base MSR prepared by embodiments of the invention 2-9, with cable jacket material and the power cable that makes, compare and can draw following result:
(1) embodiment 2 and embodiment 3 except polymeric substrate different, embodiment 3 polymeric substrates are than the embodiment many vinyl-vinyl acetate copolymers of 1 polymeric substrate (EVA), and gained sheath material embodiment 2 is than the high 0.7MPa of embodiment 1 sheath material tensile strength, proof vinyl-vinyl acetate copolymer (EVA) has better tensile strength than ethylene-methyl methacrylate methyl terpolymer (EMMA), hence one can see that, the addition of vinyl acetate copolymer (EVA) is more, and tensile strength is higher.
Meanwhile, embodiment 2 ageing-resistant performances are better than embodiment 3, prove and use ethylene-methyl methacrylate methyl terpolymer (EMMA) preparing product ageing-resistant performance to be better than the product that uses vinyl-vinyl acetate copolymer (EVA) to make.
(2) embodiment 3 and embodiment 4 are relatively, except meeting the ratio difference of oxidation inhibitor, total amount is identical, other all formulas are identical, be primary antioxidant pentaerythritol ester (antioxidant 1010) in embodiment 3: auxiliary antioxidant sulphur ester antioxidant Tyox B (anti-oxidant DLTP) is 1:1, and 1010:DLTP is 1:3 in embodiment 4, sheath material embodiment 4 aging resistance of gained are better than embodiment 3, hence one can see that, in the identical situation of oxidation inhibitor total amount, the synergistic effect of the two when auxiliary antioxidant addition is greater than primary antioxidant addition, be greater than the synergistic effect of the two addition when identical.
(3) embodiment 4 and embodiment 5 are relatively, inorganic combustion inhibitor total amount is identical, embodiment 4 adopts single magnesium hydroxide, embodiment 5 adopts composite inorganic combustion inhibitor magnesium hydroxide, aluminium hydroxide and zinc borate, and other components are identical, sheath material embodiment 5 oxygen indexs of gained are higher by 0.5 than embodiment 4, hence one can see that, in the situation that inorganic combustion inhibitor addition total amount is identical, uses product that composite inorganic combustion inhibitor makes to make product flame retarding efficiency than single inorganic combustion inhibitor high.
(4) embodiment 5 and embodiment 6 are relatively, the two all adopts composite inorganic combustion inhibitor, in embodiment 5, fire retardant aluminium hydroxide is 2.0Kg, zinc borate is 1.0kg, in embodiment 5, fire retardant aluminium hydroxide is 1.0Kg, zinc borate is 2.0Kg, and sheath material embodiment 6 oxygen indexs of gained are higher by 0.5 than embodiment 5, proves that zinc borate and nitrogenated flame retardant melamine cyanurate (MCA) have better flame retardant synergistic effect.
(5) embodiment 6 and embodiment 7,8 are relatively, in embodiment 7, anti-irradiation agent boron nitride is than the many 150g of boron nitride in embodiment 6, and the few 150g of high phenyl siloxane rubber, the few 150g of boron nitride in embodiment 8, and the many 150g of high phenyl siloxane rubber, anti-irradiation agent total amount is identical, other components are identical, gained sheath material embodiment 8 radiation resistances are best, secondly, embodiment 7 radiation resistances are the poorest, prove that high phenyl siloxane rubber radiation resistance is better than boron nitride, but high phenyl siloxane rubber price is higher than boron nitride.
(6) embodiment 6 and embodiment 9 are relatively, in embodiment 9, anti-irradiation agent adopts boron nitride and norbide composite (1:1), embodiment 6 adopts single boron nitride, total amount is identical, other components are identical, gained sheath material radiation resistance is basic identical, proves that boron nitride and norbide radiation resistance are basic identical.
Claims (65)
1. a preparation method for cable halogen-free flameproof sheath material for core, is characterized in that: it comprises the raw material of following weight part: polymeric substrate: 100 parts; Inorganic combustion inhibitor: 100-140 part; Polyphosphonitrile fire retardant: 15-25 part; Nitrogenated flame retardant: 15-30; Composite antioxidant: 4-8 part; Anti-irradiation agent: 5-15 part; Processing aid: 6-12 part;
Wherein said polymeric substrate comprises compatilizer and ethylene-methyl methacrylate methyl terpolymer;
Wherein, described compatilizer is the ethylene-vinyl acetate copolymer of radiation grafting maleic anhydride;
Described inorganic combustion inhibitor comprises magnesium hydroxide;
Described polyphosphonitrile fire retardant comprises hexaphenoxycyclotriphosphazene;
Described nitrogenated flame retardant comprises melamine cyanurate;
Described composite antioxidant comprises primary antioxidant, auxiliary antioxidant and UV light absorber;
Wherein, described primary antioxidant comprises pentaerythritol ester and/or β-(3,5-di-tert-butyl-4-hydroxy phenyl) propionic acid octadecyl ester;
Described auxiliary antioxidant comprises sulphur ester antioxidant;
Described UV light absorber comprise 2-(2'-hydroxyl-3', 5'-bis-tertiary amyl phenyl) benzotriazole, 2-(the special octyl phenyl of 2'-hydroxyl-5'-) benzotriazole and 2-(2'-hydroxyl-3', 5'-is two-α, α-
Dimethyl benzyl) phenyl) one or more in benzotriazole;
Described anti-irradiation agent comprises anti-irradiation agent A and anti-irradiation agent B, and wherein anti-irradiation agent A is high phenyl siloxane rubber and/or phenylene silicone rubber; Anti-irradiation agent B is norbide and/or boron nitride;
Described processing aid comprises crosslinking sensitizer and lubricant;
Wherein crosslinking sensitizer comprises trimethylolpropane trimethacrylate and/or iso-cyanuric acid triallyl ester, and lubricant comprises one or more in polyethylene wax, Zinic stearas and calcium stearate.
2. the preparation method of cable halogen-free flameproof sheath material for core as claimed in claim 1, is characterized in that: described ethylene-methyl methacrylate methyl terpolymer is block copolymerization; The ratio of weight and number of described compatilizer and ethylene-methyl methacrylate methyl terpolymer is (5-15): (85-95).
3. the preparation method of cable halogen-free flameproof sheath material for core as claimed in claim 2, is characterized in that: in described ethylene-methyl methacrylate methyl terpolymer, polymer unit methyl methacrylate accounts for the molar percentage 14%-40% of total polymer unit in multipolymer.
4. the preparation method of cable halogen-free flameproof sheath material for core as claimed in claim 3, is characterized in that: the melting index MI of described ethylene-methyl methacrylate methyl terpolymer is 2-6.
5. the preparation method of cable halogen-free flameproof sheath material for the core as described in any one in claim 1-4, is characterized in that:
Described polymeric substrate also comprises ethylene-vinyl acetate copolymer;
When containing ethylene-vinyl acetate copolymer, and when compatilizer is the ethylene-vinyl acetate copolymer of radiation grafting maleic anhydride, described ethylene-methyl methacrylate methyl terpolymer: the ratio of weight and number of ethylene-vinyl acetate copolymer is (70-95): (5-30).
6. the preparation method of cable halogen-free flameproof sheath material for core as claimed in claim 5, is characterized in that: described ethylene-methyl methacrylate methyl terpolymer and ethylene-vinyl acetate copolymer are block copolymerization; In described ethylene-vinyl acetate copolymer, polymer unit vinyl acetate accounts for the molar percentage 14%-40% of total polymer unit in multipolymer.
7. the preparation method of cable halogen-free flameproof sheath material for core as claimed in claim 6, is characterized in that: the melting index MI of described ethylene-vinyl acetate copolymer is 2-6.
8. the preparation method of cable halogen-free flameproof sheath material for the core as described in any one in claim 1-4, is characterized in that: described inorganic combustion inhibitor also comprises aluminium hydroxide and/or zinc borate.
9. the preparation method of cable halogen-free flameproof sheath material for core as claimed in claim 8, is characterized in that: when adding aluminium hydroxide, described magnesium hydroxide and the ratio of weight and number of aluminium hydroxide are (60-90): (40-10); When adding zinc borate, described magnesium hydroxide and the ratio of weight and number of zinc borate are (70-95): (30-5); When adding aluminium hydroxide and zinc borate, the ratio of weight and number of the addition of described magnesium hydroxide, aluminium hydroxide and zinc borate is (50-100): (5-50): (5-30) simultaneously.
10. the preparation method of cable halogen-free flameproof sheath material for core as claimed in claim 5, is characterized in that: described inorganic combustion inhibitor also comprises aluminium hydroxide and/or zinc borate.
The preparation method of cable halogen-free flameproof sheath material for 11. cores as claimed in claim 10, is characterized in that: when adding aluminium hydroxide, described magnesium hydroxide and the ratio of weight and number of aluminium hydroxide are (60-90): (40-10); When adding zinc borate, described magnesium hydroxide and the ratio of weight and number of zinc borate are (70-95): (30-5); When adding aluminium hydroxide and zinc borate, the ratio of weight and number of the addition of described magnesium hydroxide, aluminium hydroxide and zinc borate is (50-100): (5-50): (5-30) simultaneously.
The preparation method of cable halogen-free flameproof sheath material for 12. cores as described in claim 6 or 7, is characterized in that: described inorganic combustion inhibitor also comprises aluminium hydroxide and/or zinc borate.
The preparation method of cable halogen-free flameproof sheath material for 13. cores as claimed in claim 12, is characterized in that: when adding aluminium hydroxide, described magnesium hydroxide and the ratio of weight and number of aluminium hydroxide are (60-90): (40-10); When adding zinc borate, described magnesium hydroxide and the ratio of weight and number of zinc borate are (70-95): (30-5); When adding aluminium hydroxide and zinc borate, the ratio of weight and number of the addition of described magnesium hydroxide, aluminium hydroxide and zinc borate is (50-100): (5-50): (5-30) simultaneously.
The preparation method of cable halogen-free flameproof sheath material for 14. cores as described in any one in claim 1-4, is characterized in that: described sulphur ester antioxidant is the two octadecyl esters of Tyox B and/or thio-2 acid; Described UV light absorber is 2-(2'-hydroxyl-3', 5'-bis-tertiary amyl phenyl) benzotriazole.
The preparation method of cable halogen-free flameproof sheath material for 15. cores as claimed in claim 14, is characterized in that: described primary antioxidant: auxiliary antioxidant: the ratio of weight and number of the addition of UV light absorber is 1:(1-3): (0.1-0.5).
The preparation method of cable halogen-free flameproof sheath material for 16. cores as claimed in claim 5, is characterized in that: described sulphur ester antioxidant is the two octadecyl esters of Tyox B and/or thio-2 acid; Described UV light absorber is 2-(2'-hydroxyl-3', 5'-bis-tertiary amyl phenyl) benzotriazole.
The preparation method of cable halogen-free flameproof sheath material for 17. cores as claimed in claim 16, is characterized in that: described primary antioxidant: auxiliary antioxidant: the ratio of weight and number of the addition of UV light absorber is 1:(1-3): (0.1-0.5).
The preparation method of cable halogen-free flameproof sheath material for 18. cores as described in claim 6 or 7, is characterized in that: described sulphur ester antioxidant is the two octadecyl esters of Tyox B and/or thio-2 acid; Described UV light absorber is 2-(2'-hydroxyl-3', 5'-bis-tertiary amyl phenyl) benzotriazole.
The preparation method of cable halogen-free flameproof sheath material for 19. cores as claimed in claim 18, is characterized in that: described primary antioxidant: auxiliary antioxidant: the ratio of weight and number of the addition of UV light absorber is 1:(1-3): (0.1-0.5).
The preparation method of cable halogen-free flameproof sheath material for 20. cores as claimed in claim 8, is characterized in that: described sulphur ester antioxidant is the two octadecyl esters of Tyox B and/or thio-2 acid; Described UV light absorber is 2-(2'-hydroxyl-3', 5'-bis-tertiary amyl phenyl) benzotriazole.
The preparation method of cable halogen-free flameproof sheath material for 21. cores as claimed in claim 20, is characterized in that: described primary antioxidant: auxiliary antioxidant: the ratio of weight and number of the addition of UV light absorber is 1:(1-3): (0.1-0.5).
The preparation method of cable halogen-free flameproof sheath material for 22. cores as described in any one in claim 9-11 and 13, is characterized in that: described sulphur ester antioxidant is the two octadecyl esters of Tyox B and/or thio-2 acid; Described UV light absorber is 2-(2'-hydroxyl-3', 5'-bis-tertiary amyl phenyl) benzotriazole.
The preparation method of cable halogen-free flameproof sheath material for 23. cores as claimed in claim 22, is characterized in that: described primary antioxidant: auxiliary antioxidant: the ratio of weight and number of the addition of UV light absorber is 1:(1-3): (0.1-0.5).
The preparation method of cable halogen-free flameproof sheath material for 24. cores as claimed in claim 12, is characterized in that: described sulphur ester antioxidant is the two octadecyl esters of Tyox B and/or thio-2 acid; Described UV light absorber is 2-(2'-hydroxyl-3', 5'-bis-tertiary amyl phenyl) benzotriazole.
The preparation method of cable halogen-free flameproof sheath material for 25. cores as claimed in claim 24, is characterized in that: described primary antioxidant: auxiliary antioxidant: the ratio of weight and number of the addition of UV light absorber is 1:(1-3): (0.1-0.5).
The preparation method of cable halogen-free flameproof sheath material for 26. cores as described in any one in claim 1-4, is characterized in that: the parts by weight of described crosslinking sensitizer are 1-3 part, the parts by weight of described lubricant are 2-5 part.
The preparation method of cable halogen-free flameproof sheath material for 27. cores as claimed in claim 26, is characterized in that: described processing aid also comprises carbon black; The parts by weight of described carbon black are 2-4 part.
The preparation method of cable halogen-free flameproof sheath material for 28. cores as claimed in claim 5, is characterized in that: the parts by weight of described crosslinking sensitizer are 1-3 part, the parts by weight of described lubricant are 2-5 part.
The preparation method of cable halogen-free flameproof sheath material for 29. cores as claimed in claim 28, is characterized in that: described processing aid also comprises carbon black; The parts by weight of described carbon black are 2-4 part.
The preparation method of cable halogen-free flameproof sheath material for 30. cores as described in claim 6 or 7, is characterized in that: the parts by weight of described crosslinking sensitizer are 1-3 part, the parts by weight of described lubricant are 2-5 part.
The preparation method of cable halogen-free flameproof sheath material for 31. cores as claimed in claim 30, is characterized in that: described processing aid also comprises carbon black; The parts by weight of described carbon black are 2-4 part.
The preparation method of cable halogen-free flameproof sheath material for 32. cores as claimed in claim 8, is characterized in that: the parts by weight of described crosslinking sensitizer are 1-3 part, the parts by weight of described lubricant are 2-5 part.
The preparation method of cable halogen-free flameproof sheath material for 33. cores as claimed in claim 32, is characterized in that: described processing aid also comprises carbon black; The parts by weight of described carbon black are 2-4 part.
The preparation method of cable halogen-free flameproof sheath material for 34. cores as described in any one in claim 9-11 and 13, is characterized in that: the parts by weight of described crosslinking sensitizer are 1-3 part, the parts by weight of described lubricant are 2-5 part.
The preparation method of cable halogen-free flameproof sheath material for 35. cores as claimed in claim 34, is characterized in that: described processing aid also comprises carbon black; The parts by weight of described carbon black are 2-4 part.
The preparation method of cable halogen-free flameproof sheath material for 36. cores as claimed in claim 12, is characterized in that: the parts by weight of described crosslinking sensitizer are 1-3 part, the parts by weight of described lubricant are 2-5 part.
The preparation method of cable halogen-free flameproof sheath material for 37. cores as claimed in claim 36, is characterized in that: described processing aid also comprises carbon black; The parts by weight of described carbon black are 2-4 part.
The preparation method of cable halogen-free flameproof sheath material for 38. cores as claimed in claim 14, is characterized in that: the parts by weight of described crosslinking sensitizer are 1-3 part, the parts by weight of described lubricant are 2-5 part.
The preparation method of cable halogen-free flameproof sheath material for 39. cores as claimed in claim 38, is characterized in that: described processing aid also comprises carbon black; The parts by weight of described carbon black are 2-4 part.
The preparation method of cable halogen-free flameproof sheath material for 40. cores as described in any one in claim 15-17,19-21 and 23-25, is characterized in that: the parts by weight of described crosslinking sensitizer are 1-3 part, the parts by weight of described lubricant are 2-5 part.
The preparation method of cable halogen-free flameproof sheath material for 41. cores as claimed in claim 40, is characterized in that: described processing aid also comprises carbon black; The parts by weight of described carbon black are 2-4 part.
The preparation method of cable halogen-free flameproof sheath material for 42. cores as claimed in claim 18, is characterized in that: the parts by weight of described crosslinking sensitizer are 1-3 part, the parts by weight of described lubricant are 2-5 part.
The preparation method of cable halogen-free flameproof sheath material for 43. cores as claimed in claim 42, is characterized in that: described processing aid also comprises carbon black; The parts by weight of described carbon black are 2-4 part.
The preparation method of cable halogen-free flameproof sheath material for 44. cores as claimed in claim 22, is characterized in that: the parts by weight of described crosslinking sensitizer are 1-3 part, the parts by weight of described lubricant are 2-5 part.
The preparation method of cable halogen-free flameproof sheath material for 45. cores as claimed in claim 44, is characterized in that: described processing aid also comprises carbon black; The parts by weight of described carbon black are 2-4 part.
46. 1 kinds of cores as described in any one in claim 1-4 preparation method of cable halogen-free flameproof sheath material, it is characterized in that: its step comprises: polymeric substrate, inorganic combustion inhibitor, polyphosphonitrile fire retardant, nitrogenated flame retardant, composite antioxidant and anti-irradiation agent B are put into Banbury mixer mixing, after melting, add processing aid and anti-irradiation agent A, in 120～140 ℃ of temperature ranges mixing 10～20 minutes, after be promoted to twin screw extruder air-cooled extruding pelletization in 110～150 ℃ of temperature ranges;
While containing carbon black in raw material, its step comprises: polymeric substrate, inorganic combustion inhibitor, polyphosphonitrile fire retardant, nitrogenated flame retardant, composite antioxidant, anti-irradiation agent B and carbon black are put into Banbury mixer mixing, after melting, add crosslinking sensitizer, lubricant and anti-irradiation agent A, in 120～140 ℃ of temperature ranges mixing 10～20 minutes, after be promoted to twin screw extruder air-cooled extruding pelletization in 110～150 ℃ of temperature ranges.
47. 1 kinds of cores as claimed in claim 5 preparation method of cable halogen-free flameproof sheath material, it is characterized in that: its step comprises: polymeric substrate, inorganic combustion inhibitor, polyphosphonitrile fire retardant, nitrogenated flame retardant, composite antioxidant and anti-irradiation agent B are put into Banbury mixer mixing, after melting, add processing aid and anti-irradiation agent A, in 120～140 ℃ of temperature ranges mixing 10～20 minutes, after be promoted to twin screw extruder air-cooled extruding pelletization in 110～150 ℃ of temperature ranges;
While containing carbon black in raw material, its step comprises: polymeric substrate, inorganic combustion inhibitor, polyphosphonitrile fire retardant, nitrogenated flame retardant, composite antioxidant, anti-irradiation agent B and carbon black are put into Banbury mixer mixing, after melting, add crosslinking sensitizer, lubricant and anti-irradiation agent A, in 120～140 ℃ of temperature ranges mixing 10～20 minutes, after be promoted to twin screw extruder air-cooled extruding pelletization in 110～150 ℃ of temperature ranges.
48. 1 kinds of cores as described in claim 6 or 7 preparation method of cable halogen-free flameproof sheath material, it is characterized in that: its step comprises: polymeric substrate, inorganic combustion inhibitor, polyphosphonitrile fire retardant, nitrogenated flame retardant, composite antioxidant and anti-irradiation agent B are put into Banbury mixer mixing, after melting, add processing aid and anti-irradiation agent A, in 120～140 ℃ of temperature ranges mixing 10～20 minutes, after be promoted to twin screw extruder air-cooled extruding pelletization in 110～150 ℃ of temperature ranges;
While containing carbon black in raw material, its step comprises: polymeric substrate, inorganic combustion inhibitor, polyphosphonitrile fire retardant, nitrogenated flame retardant, composite antioxidant, anti-irradiation agent B and carbon black are put into Banbury mixer mixing, after melting, add crosslinking sensitizer, lubricant and anti-irradiation agent A, in 120～140 ℃ of temperature ranges mixing 10～20 minutes, after be promoted to twin screw extruder air-cooled extruding pelletization in 110～150 ℃ of temperature ranges.
49. 1 kinds of cores as claimed in claim 8 preparation method of cable halogen-free flameproof sheath material, it is characterized in that: its step comprises: polymeric substrate, inorganic combustion inhibitor, polyphosphonitrile fire retardant, nitrogenated flame retardant, composite antioxidant and anti-irradiation agent B are put into Banbury mixer mixing, after melting, add processing aid and anti-irradiation agent A, in 120～140 ℃ of temperature ranges mixing 10～20 minutes, after be promoted to twin screw extruder air-cooled extruding pelletization in 110～150 ℃ of temperature ranges;
While containing carbon black in raw material, its step comprises: polymeric substrate, inorganic combustion inhibitor, polyphosphonitrile fire retardant, nitrogenated flame retardant, composite antioxidant, anti-irradiation agent B and carbon black are put into Banbury mixer mixing, after melting, add crosslinking sensitizer, lubricant and anti-irradiation agent A, in 120～140 ℃ of temperature ranges mixing 10～20 minutes, after be promoted to twin screw extruder air-cooled extruding pelletization in 110～150 ℃ of temperature ranges.
50. 1 kinds of cores as described in any one in claim 9-11 and 13 preparation method of cable halogen-free flameproof sheath material, it is characterized in that: its step comprises: polymeric substrate, inorganic combustion inhibitor, polyphosphonitrile fire retardant, nitrogenated flame retardant, composite antioxidant and anti-irradiation agent B are put into Banbury mixer mixing, after melting, add processing aid and anti-irradiation agent A, in 120～140 ℃ of temperature ranges mixing 10～20 minutes, after be promoted to twin screw extruder air-cooled extruding pelletization in 110～150 ℃ of temperature ranges;
While containing carbon black in raw material, its step comprises: polymeric substrate, inorganic combustion inhibitor, polyphosphonitrile fire retardant, nitrogenated flame retardant, composite antioxidant, anti-irradiation agent B and carbon black are put into Banbury mixer mixing, after melting, add crosslinking sensitizer, lubricant and anti-irradiation agent A, in 120～140 ℃ of temperature ranges mixing 10～20 minutes, after be promoted to twin screw extruder air-cooled extruding pelletization in 110～150 ℃ of temperature ranges.
51. 1 kinds of cores as claimed in claim 12 preparation method of cable halogen-free flameproof sheath material, it is characterized in that: its step comprises: polymeric substrate, inorganic combustion inhibitor, polyphosphonitrile fire retardant, nitrogenated flame retardant, composite antioxidant and anti-irradiation agent B are put into Banbury mixer mixing, after melting, add processing aid and anti-irradiation agent A, in 120～140 ℃ of temperature ranges mixing 10～20 minutes, after be promoted to twin screw extruder air-cooled extruding pelletization in 110～150 ℃ of temperature ranges;
While containing carbon black in raw material, its step comprises: polymeric substrate, inorganic combustion inhibitor, polyphosphonitrile fire retardant, nitrogenated flame retardant, composite antioxidant, anti-irradiation agent B and carbon black are put into Banbury mixer mixing, after melting, add crosslinking sensitizer, lubricant and anti-irradiation agent A, in 120～140 ℃ of temperature ranges mixing 10～20 minutes, after be promoted to twin screw extruder air-cooled extruding pelletization in 110～150 ℃ of temperature ranges.
52. 1 kinds of cores as claimed in claim 14 preparation method of cable halogen-free flameproof sheath material, it is characterized in that: its step comprises: polymeric substrate, inorganic combustion inhibitor, polyphosphonitrile fire retardant, nitrogenated flame retardant, composite antioxidant and anti-irradiation agent B are put into Banbury mixer mixing, after melting, add processing aid and anti-irradiation agent A, in 120～140 ℃ of temperature ranges mixing 10～20 minutes, after be promoted to twin screw extruder air-cooled extruding pelletization in 110～150 ℃ of temperature ranges;
While containing carbon black in raw material, its step comprises: polymeric substrate, inorganic combustion inhibitor, polyphosphonitrile fire retardant, nitrogenated flame retardant, composite antioxidant, anti-irradiation agent B and carbon black are put into Banbury mixer mixing, after melting, add crosslinking sensitizer, lubricant and anti-irradiation agent A, in 120～140 ℃ of temperature ranges mixing 10～20 minutes, after be promoted to twin screw extruder air-cooled extruding pelletization in 110～150 ℃ of temperature ranges.
53. 1 kinds of cores as described in any one in claim 15-17,19-21 and 23-25 preparation method of cable halogen-free flameproof sheath material, it is characterized in that: its step comprises: polymeric substrate, inorganic combustion inhibitor, polyphosphonitrile fire retardant, nitrogenated flame retardant, composite antioxidant and anti-irradiation agent B are put into Banbury mixer mixing, after melting, add processing aid and anti-irradiation agent A, in 120～140 ℃ of temperature ranges mixing 10～20 minutes, after be promoted to twin screw extruder air-cooled extruding pelletization in 110～150 ℃ of temperature ranges;
While containing carbon black in raw material, its step comprises: polymeric substrate, inorganic combustion inhibitor, polyphosphonitrile fire retardant, nitrogenated flame retardant, composite antioxidant, anti-irradiation agent B and carbon black are put into Banbury mixer mixing, after melting, add crosslinking sensitizer, lubricant and anti-irradiation agent A, in 120～140 ℃ of temperature ranges mixing 10～20 minutes, after be promoted to twin screw extruder air-cooled extruding pelletization in 110～150 ℃ of temperature ranges.
54. 1 kinds of cores as claimed in claim 18 preparation method of cable halogen-free flameproof sheath material, it is characterized in that: its step comprises: polymeric substrate, inorganic combustion inhibitor, polyphosphonitrile fire retardant, nitrogenated flame retardant, composite antioxidant and anti-irradiation agent B are put into Banbury mixer mixing, after melting, add processing aid and anti-irradiation agent A, in 120～140 ℃ of temperature ranges mixing 10～20 minutes, after be promoted to twin screw extruder air-cooled extruding pelletization in 110～150 ℃ of temperature ranges;
While containing carbon black in raw material, its step comprises: polymeric substrate, inorganic combustion inhibitor, polyphosphonitrile fire retardant, nitrogenated flame retardant, composite antioxidant, anti-irradiation agent B and carbon black are put into Banbury mixer mixing, after melting, add crosslinking sensitizer, lubricant and anti-irradiation agent A, in 120～140 ℃ of temperature ranges mixing 10～20 minutes, after be promoted to twin screw extruder air-cooled extruding pelletization in 110～150 ℃ of temperature ranges.
55. 1 kinds of cores as claimed in claim 22 preparation method of cable halogen-free flameproof sheath material, it is characterized in that: its step comprises: polymeric substrate, inorganic combustion inhibitor, polyphosphonitrile fire retardant, nitrogenated flame retardant, composite antioxidant and anti-irradiation agent B are put into Banbury mixer mixing, after melting, add processing aid and anti-irradiation agent A, in 120～140 ℃ of temperature ranges mixing 10～20 minutes, after be promoted to twin screw extruder air-cooled extruding pelletization in 110～150 ℃ of temperature ranges;
While containing carbon black in raw material, its step comprises: polymeric substrate, inorganic combustion inhibitor, polyphosphonitrile fire retardant, nitrogenated flame retardant, composite antioxidant, anti-irradiation agent B and carbon black are put into Banbury mixer mixing, after melting, add crosslinking sensitizer, lubricant and anti-irradiation agent A, in 120～140 ℃ of temperature ranges mixing 10～20 minutes, after be promoted to twin screw extruder air-cooled extruding pelletization in 110～150 ℃ of temperature ranges.
56. 1 kinds of cores as claimed in claim 26 preparation method of cable halogen-free flameproof sheath material, it is characterized in that: its step comprises: polymeric substrate, inorganic combustion inhibitor, polyphosphonitrile fire retardant, nitrogenated flame retardant, composite antioxidant and anti-irradiation agent B are put into Banbury mixer mixing, after melting, add processing aid and anti-irradiation agent A, in 120～140 ℃ of temperature ranges mixing 10～20 minutes, after be promoted to twin screw extruder air-cooled extruding pelletization in 110～150 ℃ of temperature ranges;
While containing carbon black in raw material, its step comprises: polymeric substrate, inorganic combustion inhibitor, polyphosphonitrile fire retardant, nitrogenated flame retardant, composite antioxidant, anti-irradiation agent B and carbon black are put into Banbury mixer mixing, after melting, add crosslinking sensitizer, lubricant and anti-irradiation agent A, in 120～140 ℃ of temperature ranges mixing 10～20 minutes, after be promoted to twin screw extruder air-cooled extruding pelletization in 110～150 ℃ of temperature ranges.
57. 1 kinds of cores as described in any one in claim 27-29,31-33,35-39 and 41-45 preparation method of cable halogen-free flameproof sheath material, it is characterized in that: its step comprises: polymeric substrate, inorganic combustion inhibitor, polyphosphonitrile fire retardant, nitrogenated flame retardant, composite antioxidant and anti-irradiation agent B are put into Banbury mixer mixing, after melting, add processing aid and anti-irradiation agent A, in 120～140 ℃ of temperature ranges mixing 10～20 minutes, after be promoted to twin screw extruder air-cooled extruding pelletization in 110～150 ℃ of temperature ranges;
While containing carbon black in raw material, its step comprises: polymeric substrate, inorganic combustion inhibitor, polyphosphonitrile fire retardant, nitrogenated flame retardant, composite antioxidant, anti-irradiation agent B and carbon black are put into Banbury mixer mixing, after melting, add crosslinking sensitizer, lubricant and anti-irradiation agent A, in 120～140 ℃ of temperature ranges mixing 10～20 minutes, after be promoted to twin screw extruder air-cooled extruding pelletization in 110～150 ℃ of temperature ranges.
58. 1 kinds of cores as claimed in claim 30 preparation method of cable halogen-free flameproof sheath material, it is characterized in that: its step comprises: polymeric substrate, inorganic combustion inhibitor, polyphosphonitrile fire retardant, nitrogenated flame retardant, composite antioxidant and anti-irradiation agent B are put into Banbury mixer mixing, after melting, add processing aid and anti-irradiation agent A, in 120～140 ℃ of temperature ranges mixing 10～20 minutes, after be promoted to twin screw extruder air-cooled extruding pelletization in 110～150 ℃ of temperature ranges;
While containing carbon black in raw material, its step comprises: polymeric substrate, inorganic combustion inhibitor, polyphosphonitrile fire retardant, nitrogenated flame retardant, composite antioxidant, anti-irradiation agent B and carbon black are put into Banbury mixer mixing, after melting, add crosslinking sensitizer, lubricant and anti-irradiation agent A, in 120～140 ℃ of temperature ranges mixing 10～20 minutes, after be promoted to twin screw extruder air-cooled extruding pelletization in 110～150 ℃ of temperature ranges.
59. 1 kinds of cores as claimed in claim 34 preparation method of cable halogen-free flameproof sheath material, it is characterized in that: its step comprises: polymeric substrate, inorganic combustion inhibitor, polyphosphonitrile fire retardant, nitrogenated flame retardant, composite antioxidant and anti-irradiation agent B are put into Banbury mixer mixing, after melting, add processing aid and anti-irradiation agent A, in 120～140 ℃ of temperature ranges mixing 10～20 minutes, after be promoted to twin screw extruder air-cooled extruding pelletization in 110～150 ℃ of temperature ranges;
While containing carbon black in raw material, its step comprises: polymeric substrate, inorganic combustion inhibitor, polyphosphonitrile fire retardant, nitrogenated flame retardant, composite antioxidant, anti-irradiation agent B and carbon black are put into Banbury mixer mixing, after melting, add crosslinking sensitizer, lubricant and anti-irradiation agent A, in 120～140 ℃ of temperature ranges mixing 10～20 minutes, after be promoted to twin screw extruder air-cooled extruding pelletization in 110～150 ℃ of temperature ranges.
60. 1 kinds of cores as claimed in claim 40 preparation method of cable halogen-free flameproof sheath material, it is characterized in that: its step comprises: polymeric substrate, inorganic combustion inhibitor, polyphosphonitrile fire retardant, nitrogenated flame retardant, composite antioxidant and anti-irradiation agent B are put into Banbury mixer mixing, after melting, add processing aid and anti-irradiation agent A, in 120～140 ℃ of temperature ranges mixing 10～20 minutes, after be promoted to twin screw extruder air-cooled extruding pelletization in 110～150 ℃ of temperature ranges;
While containing carbon black in raw material, its step comprises: polymeric substrate, inorganic combustion inhibitor, polyphosphonitrile fire retardant, nitrogenated flame retardant, composite antioxidant, anti-irradiation agent B and carbon black are put into Banbury mixer mixing, after melting, add crosslinking sensitizer, lubricant and anti-irradiation agent A, in 120～140 ℃ of temperature ranges mixing 10～20 minutes, after be promoted to twin screw extruder air-cooled extruding pelletization in 110～150 ℃ of temperature ranges.
61. 1 kinds of cable halogen-free flameproof sheath materials for the core making by the preparation method of cable halogen-free flameproof sheath material by the core described in claim 1～60 any one.
62. 1 kinds of cores as claimed in claim 61 are being prepared the application in K1 class halogen-free flameproof power cable restrictive coating for core with cable halogen-free flameproof sheath material.
63. 1 kinds of cores preparation method of K1 class halogen-free flameproof power cable restrictive coating, is characterized in that: comprises the steps: the core described in claim 61 to extrude with cable halogen-free flameproof sheath material, is coated on inner core, and radiation crosslinking.
The preparation method of K1 class halogen-free flameproof power cable restrictive coating for 64. cores as described in claim 63, is characterized in that: the source of radiation of described radiation is electron beam, the irradiation dose of described radiation is 120-180KGy.
The K1 class halogen-free flameproof power cable restrictive coating for core that 65. 1 kinds of core as described in claim 63 or 64 makes by the preparation method of K1 class halogen-free flameproof power cable restrictive coating.
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| CN201210352803.4A CN102875947B (en) | 2012-09-20 | 2012-09-20 | Halogen-free flame retardant sheath material for nuclear cable, cable sheath, preparation method and application |
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| CN201210352803.4A CN102875947B (en) | 2012-09-20 | 2012-09-20 | Halogen-free flame retardant sheath material for nuclear cable, cable sheath, preparation method and application |
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| CN103059390B (en) * | 2013-02-03 | 2015-10-28 | 福建省感创精密机械有限公司 | A kind of preparation method of halogen-free flameproof PE pipe |
| CN103073775B (en) * | 2013-02-03 | 2015-07-08 | 义乌市满旺机械设备有限公司 | Preparation method for environment-friendly anti-flaming anti-static polyethylene pipeline |
| CN103059388A (en) * | 2013-02-03 | 2013-04-24 | 王达 | Halogen-free flame retardant polythene (PE) pipe |
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Effective date of registration: 20190327 Address after: 266706 Tonghe Street Office, Pingdu City, Qingdao City, Shandong Province, north of the middle end of Tongda Road Patentee after: Qingdao Zhongke Han Cable Polymer Material Co., Ltd. Address before: 201800 Baojia Highway 2019, Jiading District, Shanghai Patentee before: Shanghai Inst. of Applied Physics Chinese Academy of Sciences |
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