CN102875947A - 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 a kind of nuclear cable halogen-free flameproof sheath material, cable sheath, and its preparation method and application.
Background technology
Generation Ⅲ nuclear power such as the U.S. AP1000 of west company nuclear power generating sets, is built in China 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 cable of nuclear power and cable accessory insulation and sheath material must have good long term heat ageing performance, and (90 ℃ of lower Long Service Lifes of first and second generation nuclear power generating sets are 40 years, 90 ℃ of lower Long Service Lifes of third and fourth generation nuclear power generating sets are 60 years), the characteristics 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 the EVA material usually
2CHCOOCH
3-under the long term heat ageing effect and under a large amount of radiation exposures, produce living radical (COO-) or active ion, and chemical reaction can further occur, living radical or active ion cause DeR, crosslinking reaction, oxidizing reaction and the molecule isomerization reaction of macromolecular chain, these reactions make the material molecule reaction rate accelerates, and sheath material can become fragile, the mechanical property variation, particularly the elongation at break of material declines to a great extent, and affects materials'use.
In addition, be inflammable macromolecular material as the vinyl-vinyl acetate copolymer of polymeric substrate, reach cable category-A bunchy vertical combustion in order to make sheath material, 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%.Mechanical property all can not satisfy the basic demand of nuclear power K1 sheath material behind the so many fire retardant of general Material Addition, in polymeric substrate, add exactly Its Compatibilizing Technology for the most effective way of mechanical property that improves material, usually 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 anti-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 satisfy the cable-flame retardant standard, namely single vertical combustion standard certainly will need to add a large amount of inorganic combustion inhibitors, affects the sheath material mechanical property, and this problem also needs to be resolved hurrily.
Summary of the invention
Technical problem to be solved by this invention is to overcome the defective 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, a kind of preparation method and application that examine with cable halogen-free flameproof sheath material, cable sheath are provided, sheath material superior performance of the present invention, have good flame retardant properties, stable radiation-resistant property, electric property and mechanical property.
One of technical scheme of the present invention is that a kind of preparation method who examines 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'-two 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 the 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 the calcium stearate.
Better, nuclear 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.
Nuclear of the present invention is with the polymkeric substance of cable halogen-free flameproof sheath material: the ratio of the parts by weight of halogen-free flame retardants reaches about 1:1.5, be that the halogen-free flame retardants addition accounts for about 60%, in order to improve the mechanical property of material, sheath material of the present invention adopt have know the preparation of intellecture property (ZL20061002875.5) radiation grafting technology the ethylene-vinyl acetate copolymer with maleic anhydride functional group (EVA-g-MAH) as compatilizer (percentage of grafting 〉=1%), this compatilizer has higher percentage of grafting, make polymeric substrate and halogen-free flame retardants that better consistency be arranged, have better mechanical property than the sheath material that adds the chemical compatibility agent.
Better among the present invention, 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: 1 ~ 5 part maleic anhydride is dissolved in the acetone, mix with 100 parts of ethylene-vinyl acetate copolymers, Deng granulation in twin screw extruder after the acetone volatilization, carry out radiation at rumbatron electron rays or gamma-rays again, radiation dose is 5 ~ 30KGy.
Better among the present invention, 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).
Better among the present invention, polymer unit methyl methacrylate (MMA) accounts for the molar percentage 14%-40% of total polymer unit in the multipolymer in the ethylene-methyl methacrylate methyl terpolymer (EMMA); Better, the melting index MI of ethylene-methyl methacrylate methyl terpolymer (EMMA) is 2-6;
Better among the present invention, described polymeric substrate also comprises ethylene-vinyl acetate copolymer (EVA); When containing ethylene-vinyl acetate copolymer (EVA), and when compatilizer was 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) was (70-95): (5-30).
Among the present invention, better described ethylene-methyl methacrylate methyl terpolymer (EMMA) and ethylene-vinyl acetate copolymer (EVA) are block copolymerization;
Among the present invention, better, polymer unit vinyl acetate (VA) accounts for the molar percentage 14%-40% of total polymer unit in the multipolymer in the ethylene-vinyl acetate copolymer (EVA); Better, the melting index MI of ethylene-vinyl acetate copolymer (EVA) is 2-6.
Better among the present invention, described inorganic combustion inhibitor can also comprise aluminium hydroxide and/or zinc borate; Better, when adding aluminium hydroxide, the ratio of weight and number of described magnesium hydroxide and aluminium hydroxide is (60-90): (40-10); When adding zinc borate, the ratio of weight and number of described magnesium hydroxide and zinc borate is (70-95): (30-5); When adding aluminium hydroxide and zinc borate simultaneously, 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).
Among the present invention, better, the preparation method of described hexaphenoxycyclotriphosphazene can reference:
1, Halogen efficient flame-retarding agent HPCTP's is synthetic, and Yang Xin changes etc., and representation and application research-phenetic analysis is Chinese 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 under nitrogen protection, adds 2kg phenol, 10L chlorobenzene, 200g polyoxyethylene glycol, 45% (weight percent); 120 ~ 130 ℃ of temperature of reaction; 8 ~ 12 hours reaction times; react complete after; carry out after component distillation divides water outlet, it is stand-by that reactant is cooled to room temperature.
2) in the phenol sodium salt for preparing, the preparation of hexaphenoxycyclotriphosphazene: in step 1); under nitrogen protection, add 30% chlorobenzene solution that contains the 1.16kg hexachlorocyclotriphosphazene; reacted 6 ~ 12 hours under 130 ~ 132 ℃ of conditions, cooling is filtered; the filtrate decompression distillation; reclaim the solvent chlorobenzene, in resultant product, add hot ethanol, washing; dry hexaphenoxycyclotriphosphazene 2.04kg, the productive rate 88% of getting of suction filtration.
Among the present invention, better, described sulphur ester antioxidant is the two octadecyl esters (oxidation inhibitor DSTP) of Tyox B (anti-oxidant DLTP) and/or thio-2 acid.
Among the present invention, better, described UV light absorber is 2-(2'-hydroxyl-3', 5'-two tertiary amyl phenyl) benzotriazole (UV-328).
Better among the present invention, 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).
Better among the present invention, the parts by weight of described crosslinking sensitizer are 1-3 part, and the parts by weight of described lubricant are 2-5 part.
Better among the present invention, described processing aid also comprises carbon black; The parts by weight of described carbon black are 2-4 part.
Better, 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, add processing aid and anti-irradiation agent A after the melting, 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, get final product;
When containing carbon black in the 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, add crosslinking sensitizer, lubricant and anti-irradiation agent A after the melting, 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 and get final product.
Among 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 industry company limited.
Two of technical scheme of the present invention is the nuclear that provides aforesaid method to make cable halogen-free flameproof sheath material.
Three of technical scheme of the present invention is that the nuclear that provides aforesaid method to make is used the application of K1 class halogen-free flameproof power cable restrictive coating at preparation nuclear with cable halogen-free flameproof sheath material.
Better, halogen-free flameproof sheath material of the present invention can be for the preparation of the insulated cable layer of the employing nuclear that is coated on three cores with the preparation of cable halogen-free flame retardant insulation material.Four of technical scheme of the present invention is that the preparation method of above-mentioned nuclear with K1 class halogen-free flameproof power cable restrictive coating is provided.The method is: nuclear of the present invention is extruded with cable halogen-free flameproof sheath material, be coated on inner core, radiation crosslinking gets final product.
Better, the source of radiation of described radiation is electron beam, 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 nuclear that is made by technique scheme four described methods K1 class halogen-free flameproof power cable restrictive coating is provided.
On the basis that meets this area general knowledge, above-mentioned each optimum condition, but arbitrary combination namely get the preferred embodiments of the invention.
Agents useful for same of the present invention and raw material be commercially available getting all.
Positive progressive effect of the present invention is: the nuclear that the present invention makes protects the material superior performance with the cable halogen-free flameproof, has good flame retardant properties, stable radiation-resistant property, electric property and mechanical property.The process 1-10KGy/h of the power cable of sheath material preparation of the present invention, integral dose 1500KGy
60The elongation at break of material remains on more than 50% behind the Cov-radiation exposure, and radiation hardness dosage can reach more than the 1500KGy simultaneously, can test by LOCK through the cable of thermal ageing and radiation aging.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 the nuclear environment, reduce the splitting of chain that the intermolecular C-C key of polymer materials causes because being stimulated, prolonged material in nuclear environment lower work-ing life.In material prescription, introduce simultaneously high efficiency composition oxidation inhibitor, intercepted free radical and generated new free radical as intermediate and polymkeric substance, thus control degradation speed, and through the reckoning of Arrhenius equation, material can use more than 60 years under 90 ℃ of temperature.
Embodiment
Mode below by embodiment further specifies the present invention, but does not therefore limit the present invention among the described scope of embodiments.The experimental technique of unreceipted actual conditions in the following example according to ordinary method and condition, or is selected according to catalogue.
In the 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 industry company limited;
Boron nitride: Yingkou Liao Bin Fine Chemical Co., Ltd;
Norbide: Mudanjiang professional production norbide company limited;
Polyethylene wax: the glad haze chemical industry in Shanghai company limited
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; add 10Kg phenol, 50L chlorobenzene, 1Kg polyoxyethylene glycol, 45% sodium hydroxide solution under the nitrogen protection; the sodium hydroxide that wherein contains 10mol; temperature of reaction 120-130 ℃; reaction times 8-12 hour; react complete after, carry out after component distillation divides water outlet, it is stand-by that reactant is cooled to room temperature.
2), the preparation of hexaphenoxycyclotriphosphazene: in step 1) in the phenol sodium salt of preparation; 30% chlorobenzene solution that under nitrogen protection, adds the hexachlorocyclotriphosphazene that contains commercial 5.8Kg; reaction is 6-12 hour under 130-132 ℃ of temperature, and cooling is filtered; filtrate is carried out underpressure distillation; reclaim the solvent chlorobenzene, in resultant product, add hot ethanol, washing; dry hexaphenoxycyclotriphosphazene 9.6Kg, the productive rate 82.8% of getting of suction filtration.
Embodiment 2
Raw material:
Wherein, used polyphosphonitrile fire retardant is the hexaphenoxycyclotriphosphazene that makes among the embodiment 1.
Operation steps:
(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 with compatilizer EVA-g-MAH, ethylene-methyl methacrylate methyl terpolymer, during banburying to 130 ℃, add high phenyl siloxane rubber (phenyl content 40%, Zinic stearas, triallyl isocyanurate (TAIC), (120-140 ℃ of banburying temperature) turnover internal mixer after mixing 10 minutes is poured material in the lift into and to be promoted to
Twin screw extruder, air-cooled at 110-150 ℃ of extruding pelletization, obtain nuclear power K1 halogen-free flameproof sheath material.
Embodiment 3
Raw material:
Wherein, used polyphosphonitrile fire retardant is the hexaphenoxycyclotriphosphazene that makes among the embodiment 1.
Operation steps:
With 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), (120-140 ℃ of banburying temperature) turnover internal mixer after mixing 10 minutes is poured material in the lift into and to be promoted to
Twin screw extruder, air-cooled at 110-150 ℃ of extruding pelletization, obtain nuclear power K1 halogen-free flameproof sheath material.
Embodiment 4
Raw material:
Wherein, used polyphosphonitrile fire retardant is the hexaphenoxycyclotriphosphazene that makes among the 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), (120-140 ℃ of banburying temperature) turnover internal mixer after mixing 10 minutes is poured material in the lift into and to be promoted to
Twin screw extruder, air-cooled at 110-150 ℃ of extruding pelletization, obtain nuclear power K1 halogen-free flameproof sheath material.
Embodiment 5
Raw material:
Wherein, used polyphosphonitrile fire retardant is the hexaphenoxycyclotriphosphazene that makes among the embodiment 1.
Operation steps:
With 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 refines (120-140 ℃ of banburying temperature) turnover internal mixer after 10 minutes, material is poured in the lift be promoted to
Twin screw extruder, air-cooled at 110-150 ℃ of extruding pelletization, obtain nuclear power K1 halogen-free flameproof sheath material.
Embodiment 6
Raw material:
Wherein, used polyphosphonitrile fire retardant is the hexaphenoxycyclotriphosphazene that makes among the embodiment 1.
Operation steps:
With 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 (120-140 ℃ of banburying temperature) turnover internal mixer after mixing 10 minutes, material is poured in the lift be promoted to
Twin screw extruder, air-cooled at 110-150 ℃ of extruding pelletization, obtain nuclear power K1 halogen-free flameproof sheath material.
Embodiment 7
Raw material:
Wherein, used polyphosphonitrile fire retardant is the hexaphenoxycyclotriphosphazene that makes among the embodiment 1.
Operation steps:
With 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 (120-140 ℃ of banburying temperature) turnover internal mixer after mixing 10 minutes, material is poured in the lift be promoted to
Twin screw extruder, air-cooled at 110-150 ℃ of extruding pelletization, obtain nuclear power K1 halogen-free flameproof sheath material.
Embodiment 8
Raw material:
Wherein, used polyphosphonitrile fire retardant is the hexaphenoxycyclotriphosphazene that makes among the embodiment 1.
Operation steps:
With 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 (120-140 ℃ of banburying temperature) turnover internal mixer after mixing 10 minutes, material is poured in the lift be promoted to
Twin screw extruder, air-cooled at 110-150 ℃ of extruding pelletization, obtain nuclear power K1 halogen-free flameproof sheath material.
Embodiment 9
Raw material:
Wherein, used polyphosphonitrile fire retardant is the hexaphenoxycyclotriphosphazene that makes among the embodiment 1.
Operation steps:
With 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 (120-140 ℃ of banburying temperature) turnover internal mixer after mixing 10 minutes, material is poured in the lift be promoted to
Twin screw extruder, air-cooled at 110-150 ℃ of extruding pelletization, obtain nuclear power K1 halogen-free flameproof sheath material.
Embodiment 10
Anti-irradiation agent in the 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 the 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 the 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 the single screw extrusion machine group, the employing nuclear insulated cable layer of cable halogen-free flame retardant insulation material preparation that is coated on three cores, by the rumbatron radiation crosslinking, dosage 120-180KGy prepares nuclear power K1 halogen-free flameproof restrictive coating.
Table 1: the test method of each test event for reaching standard is:
Table 2: sheath material and cable performance
By being compared with cable jacket material and the power cable that makes, the thorium base MSR of embodiments of the invention 2-9 preparation can draw following result:
(1) embodiment 2 is different except polymeric substrate with embodiment 3, embodiment 3 polymeric substrates many vinyl-vinyl acetate copolymer (EVA) than embodiment 1 polymeric substrate, 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.
Simultaneously, embodiment 2 ageing-resistant performances are better than embodiment 3, prove to 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 prescriptions are identical, be primary antioxidant pentaerythritol ester (antioxidant 1010) among the embodiment 3: auxiliary antioxidant sulphur ester antioxidant Tyox B (anti-oxidant DLTP) is 1:1, and 1010:DLTP is 1:3 among the 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, auxiliary antioxidant addition the two synergistic effect during greater than the primary antioxidant addition, the synergistic effect when identical greater than the two addition.
(3) embodiment 4 and embodiment 5 are relatively, the 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, it is high that the product that uses composite inorganic combustion inhibitor to make makes the product flame retarding efficiency than single inorganic combustion inhibitor.
(4) embodiment 5 and embodiment 6 are relatively, the two all adopts composite inorganic combustion inhibitor, fire retardant aluminium hydroxide is 2.0Kg among the embodiment 5, zinc borate is 1.0kg, fire retardant aluminium hydroxide is 1.0Kg among the embodiment 5, 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, anti-irradiation agent boron nitride manys 150g than boron nitride among the embodiment 6 among the embodiment 7, and the few 150g of high phenyl siloxane rubber, the few 150g of boron nitride among the 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, boron nitride and norbide composite (1:1) are adopted in anti-irradiation agent among the embodiment 9, 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 (12)
1. examine the preparation method who uses cable halogen-free flameproof sheath material for one kind, it 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 comprises 2-(2'-hydroxyl-3', 5'-two tertiary amyl phenyl) one or more in benzotriazole, 2-(the special octyl phenyl of 2'-hydroxyl-5'-) benzotriazole and 2-(2'-hydroxyl-3', two (a, the a-dimethyl benzyl) phenyl of the 5'-) 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 the calcium stearate.
2. nuclear as claimed in claim 1 is with the preparation method of cable halogen-free flameproof sheath material, and it 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);
Better, the polymer unit methyl methacrylate accounts for the molar percentage 14%-40% of total polymer unit in the multipolymer in the ethylene-methyl methacrylate methyl terpolymer; Better, the melting index MI of ethylene-methyl methacrylate methyl terpolymer is 2-6.
3. use the preparation method of cable halogen-free flameproof sheath material such as each described nuclear among the claim 1-2, it is characterized in that:
Described polymeric substrate also comprises ethylene-vinyl acetate copolymer;
When containing ethylene-vinyl acetate copolymer, and when compatilizer was 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 was (70-95): (5-30);
Better described ethylene-methyl methacrylate methyl terpolymer and ethylene-vinyl acetate copolymer are block copolymerization;
Better, the polymer unit vinyl acetate accounts for the molar percentage 14%-40% of total polymer unit in the multipolymer in the ethylene-vinyl acetate copolymer; Better, the melting index MI of ethylene-vinyl acetate copolymer is 2-6.
4. use the preparation method of cable halogen-free flameproof sheath material such as each described nuclear among the claim 1-3, it is characterized in that: described inorganic combustion inhibitor also comprises aluminium hydroxide and/or zinc borate; Better,
When adding aluminium hydroxide, the ratio of weight and number of described magnesium hydroxide and aluminium hydroxide is (60-90): (40-10);
When adding zinc borate, the ratio of weight and number of described magnesium hydroxide and zinc borate is (70-95): (30-5);
When adding aluminium hydroxide and zinc borate simultaneously, 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).
5. use the preparation method of cable halogen-free flameproof sheath material such as each described nuclear among the claim 1-4, it 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'-two tertiary amyl phenyl) benzotriazole;
Better, 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).
6. use the preparation method of cable halogen-free flameproof sheath material such as each described nuclear among the claim 1-5, it is characterized in that: the parts by weight of described crosslinking sensitizer are 1-3 part, and the parts by weight of described lubricant are 2-5 part;
Better, described processing aid also comprises carbon black; The parts by weight of described carbon black are 2-4 part.
One kind such as each described nuclear among the claim 1-6 with the 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, add processing aid and anti-irradiation agent A after the melting, 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, get final product;
When containing carbon black in the 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, add crosslinking sensitizer, lubricant and anti-irradiation agent A after the melting, 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 and get final product.
8. a nuclear that makes with the preparation method of cable halogen-free flameproof sheath material by each described nuclear of claim 1 ~ 7 is with cable halogen-free flameproof sheath material.
9. a nuclear as claimed in claim 8 is examined with the application in the K1 class halogen-free flameproof power cable restrictive coating in preparation with cable halogen-free flameproof sheath material.
10. examine the preparation method who uses K1 class halogen-free flameproof power cable restrictive coating for one kind, it is characterized in that: comprise the steps: nuclear claimed in claim 8 is extruded with cable halogen-free flameproof sheath material, be coated on inner core, radiation crosslinking gets final product.
11. the nuclear as claimed in claim 10 preparation method of K1 class halogen-free flameproof power cable restrictive coating, it is characterized in that: the source of radiation of described radiation is electron beam, and the irradiation dose of described radiation is 120-180Kgy.
12. a nuclear that makes with the preparation method of K1 class halogen-free flameproof power cable restrictive coating such as claim 10 or 11 described nuclears is with K1 class halogen-free flameproof power cable restrictive coating.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002057379A1 (en) * | 2001-01-18 | 2002-07-25 | 3M Innovative Properties Company | Water dispersed primers |
| CN101100537A (en) * | 2006-07-07 | 2008-01-09 | 中国科学院上海应用物理研究所 | Low-smoke halide-free fireproof polyolefine material and its preparation method and application |
| CN101402766A (en) * | 2008-11-10 | 2009-04-08 | 上海金发科技发展有限公司 | Polypropylene/polystyrene alloy and method of producing the same |
-
2012
- 2012-09-20 CN CN201210352803.4A patent/CN102875947B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002057379A1 (en) * | 2001-01-18 | 2002-07-25 | 3M Innovative Properties Company | Water dispersed primers |
| CN101100537A (en) * | 2006-07-07 | 2008-01-09 | 中国科学院上海应用物理研究所 | Low-smoke halide-free fireproof polyolefine material and its preparation method and application |
| CN101402766A (en) * | 2008-11-10 | 2009-04-08 | 上海金发科技发展有限公司 | Polypropylene/polystyrene alloy and method of producing the same |
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