WO2015043122A1 - Zero halogen sheath material for 125°c irradiation cross-linked epcv photovoltaics, and method for preparation thereof - Google Patents

Zero halogen sheath material for 125°c irradiation cross-linked epcv photovoltaics, and method for preparation thereof Download PDF

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Publication number
WO2015043122A1
WO2015043122A1 PCT/CN2014/070594 CN2014070594W WO2015043122A1 WO 2015043122 A1 WO2015043122 A1 WO 2015043122A1 CN 2014070594 W CN2014070594 W CN 2014070594W WO 2015043122 A1 WO2015043122 A1 WO 2015043122A1
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parts
zone
weight
sheath material
halogen
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PCT/CN2014/070594
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French (fr)
Chinese (zh)
Inventor
罗超华
范伟伟
范魏魏
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江苏达胜高聚物有限公司
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Publication of WO2015043122A1 publication Critical patent/WO2015043122A1/en

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    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
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Definitions

  • the invention relates to a low-smoke halogen-free power cable material and a preparation method thereof, in particular to a 125°C radiation cross-linked EPCV photovoltaic low-smoke halogen-free flame-retardant sheath material and a preparation method thereof.
  • photovoltaic wire and cable As an important part of the photovoltaic industry, photovoltaic wire and cable, its safety and reliability are crucial for photovoltaic power generation systems, and the safety and reliability of photovoltaic cables are mainly determined by photovoltaic cable materials.
  • photovoltaic cable materials At present, the most widely used in the field of photovoltaic cables is XLPE materials. XLPE-type photovoltaic cable materials have high hardness in the application process, inconvenient installation in a small space, and can not achieve low flame-free halogen-free VW-1 flame retardant level.
  • EPCV is a blend of rubber and plastic with excellent rubber elasticity and high filling properties as well as excellent mechanical and processing properties of plastics. It is applied to photovoltaic cables, which not only has excellent mechanical and electrical properties, but also has excellent flame retardant properties and excellent oil-repellent properties. It can achieve halogen-free flame retardant VW-1 grade, and does not contain phosphorus-nitrogen flame retardant. The amount of smoke released during the combustion process is extremely low, and it is truly green. Therefore, the 125° CEPCV photovoltaic low-smoke halogen-free sheath material has very good economic and social benefits.
  • CN102766293A discloses an irradiation cross-linked low-smoke halogen-free and non-red phosphorus flame retardant material, including: 10 to 80 parts by weight of an ene-vinyl acetate copolymer; 5 to 30 parts by weight of an ethylene-octene copolymer and/or an ethylene-butene copolymer and/or an ethylene propylene diene rubber; 0 to 100 parts by weight of a polyethylene; 1-20 parts by weight of the polymer compatibilizer; 0.5-10 parts by weight of the silicone polymer; 1-10 parts by weight of the composite antioxidant; aluminum hydroxide and/or magnesium hydroxide and/or modified aluminum hydroxide and/or Or modified magnesium hydroxide 0-200 parts by weight; high molecular weight ammonium polyphosphate 0.1-100 parts by weight and / or phosphate flame retardant 0.1-50 parts by weight and / or melamine cyanurate 0.1-50 parts by weight, It is applied to the heat-
  • an object of the present invention is to provide a halogen-free flame-retardant sheath material for 125 ° C irradiation cross-linked EPCV photovoltaic, which has excellent oil-proof performance and Flame retardant performance, extremely low smoke emission during combustion, high light transmittance in smoke, and excellent mechanical and electrical properties.
  • a 125 ° C irradiation cross-linked EPCV photovoltaic halogen-free flame-retardant sheath material which is mainly made up of the following raw materials by weight:
  • the parts by weight of the ethylene propylene diene monomer are, for example, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts or 19 parts.
  • thermoplastic elastomer is, for example, 0.5 parts by weight, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts or 4.5 parts by weight.
  • the parts by weight of the polyethylene are, for example, 1 part, 3 parts, 5 parts, 7 parts, 9 parts, 11 parts, 13 parts, 15 parts, 17 parts, 19 parts, 21 parts or 23 parts.
  • the parts by weight of the ethylene-vinyl acetate copolymer are, for example, 0.5 part, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts or 9 parts.
  • the parts by weight of the compatibilizer are, for example, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts or 4.5 parts.
  • the parts by weight of the aluminum hydroxide are, for example, 47 parts, 49 parts, 51 parts, 52 parts, 54 parts, 57 parts, 60 parts or 63 parts.
  • the stabilizer is, for example, 1.2 parts, 1.5 parts, 1.8 parts, 2.1 parts, 2.4 parts, 2.7 parts or 2.9 parts by weight.
  • the parts by weight of the silicone master batch are, for example, 1.2 parts, 1.5 parts, 1.8 parts, 2.1 parts, 2.4 parts, 2.7 parts or 2.9 parts.
  • a 125 ° C radiation crosslinked EPCV photovoltaic halogen-free flame-retardant sheath material is mainly made up of the following raw materials by weight:
  • a 125 ° C irradiation cross-linked EPCV photovoltaic halogen-free flame-retardant sheath material the weight of which is mainly made of the following materials:
  • the above-mentioned 125 ° C irradiation cross-linked EPCV photovoltaic halogen-free flame-retardant sheath material can be obtained by blending and granulating a predetermined amount of raw materials through a conventional internal mixer and extruding and granulating the extruder.
  • the ethylene propylene rubber (EPDM) ethylene propylene segment molar ratio is 60:40 ⁇ 70:30
  • the third monomer is ethylidene borneene
  • the third monomer accounts for the total mass of the three monomers.
  • the mass percentage is 1 to 3%
  • the number average molecular weight is 5 to 150,000
  • the Mooney viscosity at 100 ° C is 30 to 70 Pa s
  • the Shore A hardness is 20 to 50.
  • the thermoplastic elastomer is an ethylene-propylene copolymer having a number average molecular weight of 10 to 200,000, a Mooney viscosity of 100 to 60 Pa-s at 100 ° C, and a Shore A hardness of 30 to 60.
  • the melt index at 190 ° C and 2.16 kg is 1 to 5 g/10 min.
  • the polyethylene is a low density polyethylene having a number average molecular weight of 5 to 150,000, and a melt index of 1 to 5 g/10 min at 190 ° C and 2.16 kg.
  • the ethylene-vinyl acetate copolymer has a vinyl acetate content of 40 to 60% by weight, and a melt index of 3 to 5 g/10 min at 190 ° C and 2.16 kg.
  • the compatibilizing agent is maleic anhydride grafted polyethylene, the graft ratio is 1 to 2%, and the melt index at 190 ° C and 2.16 kg is 1 to 3 g/10 min.
  • the aluminum hydroxide is prepared by a Bayer-sintering combination process.
  • the aluminum hydroxide is modified with aminosilicone, and has a particle diameter D50 of 1 to 2 ⁇ m and a mesh number of 4000 to 8000 mesh.
  • the stabilizer is composed of the following components in parts by weight: 35 to 55 parts of calcium stearate, 5 to 35 parts of zinc stearate, and four [ ⁇ -(3,5-di-tert-butyl-4) -Hydroxyphenyl)propionate] pentaerythritol ester 35 to 60 parts.
  • the silicone masterbatch is composed of the following components in parts by weight: 10 to 20 parts of low density polyethylene, 45 to 75 parts of siloxane, 15 to 55 parts of silica.
  • the low-density polyethylene has a number average molecular weight of 5 to 100,000, and a melt index of 5 to 10 g/10 min at 190 ° C and 2.16 kg.
  • the siloxane is methyl vinyl siloxane, and the number average molecular weight is from 60 to 1,000,000.
  • the silica is precipitated silica having a mesh number of 5000 to 6000 mesh.
  • the second object of the present invention is to provide a method for preparing a 125 ° C irradiation crosslinked EPCV photovoltaic low-smoke halogen-free flame-retardant sheath material as described above, which is blended and granulated by an internal mixer, and extruded by an extruder. After granulation, the 125 ° C irradiation crosslinked EPCV photovoltaic low-smoke halogen-free flame-retardant sheath material of the present invention can be obtained.
  • the components of the formula amount are melt-blended by an internal mixer, and then granulated by a single-screw extruder;
  • the mixing temperature of the step (1) is 160 to 175 ° C, and the mixing time is 15 to 25 minutes.
  • the mixing temperature is, for example, 162 ° C, 164 ° C, 166 ° C, 168 ° C, 170 ° C, 172 ° C or 174 ° C.
  • the mixing time is, for example, 16 minutes, 17 minutes, 18 minutes, 19 minutes, 20 minutes, 2 minutes, 22 minutes, 23 minutes or 24 minutes.
  • the single-screw extruder of the step (1) is divided into seven zones, and the working temperature of each zone is: one zone 110 ⁇ 115°C, the second zone 115 ⁇ 120°C, the third zone 115 ⁇ 120° C, the fourth zone is 120 to 125 ° C, the fifth zone is 120 to 125 ° C, the sixth zone is 120 to 130 ° C, and the seventh zone is 125 to 130 ° C.
  • the temperature of the first zone is, for example, 110.5 ° C, bubble, 111.5 ° C, 112 ° C, 112.5 ° C, 113 ° C 113.5 ° C, 114 ° C or 114.5 ° Co.
  • the temperature of the second zone is, for example, 115.5 ° C, 116 ° C, 116.5 ° C, 117 ° C, 117.5 ° C, 118 ° C 118.5 ° C, 119 ° C or 119.5 ° C.
  • the temperature of the third zone is, for example, 115.5 ° C, 116 ° C, 116.5 ° C, 117 ° C, 117.5 ° C, 118 ° C 118.5 ° C, 119 ° C or 119.5 ° C.
  • the temperature of the fourth zone is, for example, 120.5 ° C, 121 ° C, 121.5 ° C, 122 ° C, 122.5 ° C, 123 ° C 123.5 ° C, 124 ° C or 124.5 ° C.
  • the temperature of the fifth zone is, for example, 120.5 ° C, 121 ° C, 121.5 ° C, 122 ° C, 122.5 ° C, 123 ° C 123.5 ° C, 124 ° C or 124.5 ° C.
  • the temperature of the sixth zone is, for example, 121 ° C, 122 ° C, 123 ° C, 124 ° C, 125 ° C, 126 ° C, 127 ° C, 128 ° C or 129 ° C.
  • the temperature of the seventh zone is, for example, 125.5 ° C, 126 ° C, 126.5 ° C, 127 ° C, 127.5 ° C, 128 ° C 128.5 ° C, 129 ° C or 129.5 ° C.
  • the extruder in the step (2) is divided into four zones, and the operating temperature of each zone is:
  • the second zone is 165 to 175 ° C
  • the third zone is 165 to 175 ° C
  • the fourth zone is 170 to 180 ° C.
  • the temperature of the first zone is, for example, 151 ° C, 152 ° C, 153 ° C, 154 ° C, 155 ° C, 156 ° C, 157 ° C, 158 ° C or 159 ° C.
  • the temperature of the second zone is, for example, 166 ° C, 167 ° C, 168 ° C, 169 ° C, 170 ° C, 171 ° C, 172 ° C, 173 ° C or 174 ° C.
  • the temperature of the third zone is, for example, 166 ° C, 167 ° C, 168 ° C, 169 ° C, 170 ° C, 171 ° C, 172 ° C, 173 ° C or 174 ° C.
  • the temperature of the fourth zone is, for example, 171 ° C, 172 ° C, 173 ° C, 174 ° C, 175 ° C, 176 ° C, 177 ° C, 178 ° C or 179 ° C.
  • the present invention has the following beneficial effects:
  • the product of the present invention has excellent flame retardancy and oil repellency, can achieve halogen-free flame retardant VW-1, and can pass the oil-proof requirements of UL44.
  • the product of the invention has very low smoke emission during combustion, and the light transmittance in the smoke can reach more than 90%, and has excellent mechanical properties and weather resistance, and fully meets the performance requirements of the UL4703-2010 standard.
  • a low-smoke halogen-free sheathed cable material for 125 ° C irradiation cross-linked EPCV photovoltaic mainly made of the following raw materials by weight: EPDM: 15 parts; thermoplastic elastomer (TPE) : 1 part; Polyethylene: 5 parts; Ethylene-vinyl acetate copolymer: 10 parts; Compatibilizer: 2; 63 parts of aluminum hydroxide; Stabilizer: 2 parts; Silicone masterbatch: 2 parts.
  • the ethylene propylene rubber (EPDM) ethylene propylene segment molar ratio is 60:40
  • the third monomer is ethylidene norbornene
  • the third monomer accounts for 3% by mass of the total mass of the three monomers.
  • the number average molecular weight is 150,000
  • the Mooney viscosity at 100 °C is 50 Pa's
  • the Shore A hardness is 40.
  • the thermoplastic elastomer (TPE) is an ethylene-propylene copolymer having a number average molecular weight of 150,000, a Mooney viscosity at 100 ° C of 50 Pa s, a Shore A hardness of 60, a melt index at 190 ° C and 2.16 kg. It is 1 ⁇ 5 g/10min.
  • the polyethylene is a low density polyethylene having a number average molecular weight of 80,000, a melting index of 5 g/10 mino at 190 ° C and 2.16 kg.
  • the ethylene-vinyl acetate copolymer had a vinyl acetate content of 50% by weight, and a melting index of 5 g/10 min at 190 ° C and 2.16 kg.
  • the compatibilizer was maleic anhydride grafted polyethylene having a graft ratio of 2%, a melt index of 2 g/10 min at 190 ° C and 2.16 kg.
  • the aluminum hydroxide is prepared by a Bayer-sintering combination method and is modified by aminosilicone, and has a particle diameter D50 of 2 ⁇ m and a mesh number of 5,000 mesh.
  • the stabilizer is composed of the following components in parts by weight: calcium stearate: 40 parts, zinc stearate: 10 parts, tetra [ ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl) Propionate] pentaerythritol ester: 50 parts.
  • the silicone masterbatch is composed by weight of the following components: Low density polyethylene: 10 parts, siloxane: 50 parts, silica: 40 parts.
  • the low density polyethylene has a number average molecular weight of 50,000, a melt index of 5 g/10 min at 190 ° C and 2.16 kg.
  • the siloxane is methyl vinyl siloxane with a number average molecular weight of 800,000.
  • the silica was precipitated silica having a mesh number of 6,000 mesh.
  • the above method for preparing 125 ° C radiation cross-linked EPCV photovoltaic low-smoke halogen-free sheathed cable material comprises the steps of:
  • the extruded particles are extruded through an extruder.
  • the wire is irradiated and crosslinked by an electron accelerator.
  • the components are melt blended by an internal mixer.
  • the specific parameters are: the mixing temperature is 160-175 ° C, and the mixing time is 15-25 minutes.
  • the single-screw extruder is divided into seven zones, and the operating temperatures of the zones are: 110-115 ° C in the first zone, 115-120 ° C in the second zone, and 115-120 ° in the third zone.
  • the fourth zone is 120-125 °C
  • the fifth zone is 120-125 °C
  • the sixth zone is 120-130 °C
  • the seventh zone is 125-130 °C.
  • the extruder is divided into four zones, and the operating temperatures of the zones are: 150-160 ° C in the first zone, 165-175 ° C in the second zone, and 165-175 ° C in the third zone.
  • the fourth zone is 170-180 °C.
  • EPDM 12 parts
  • thermoplastic elastomer (TPE) 2 parts
  • Polyethylene 10 parts
  • Ethylene-vinyl acetate copolymer 10 parts
  • Compatibilizer 2; 60 parts of aluminum hydroxide
  • Stabilizer 2 parts
  • Silicone masterbatch 2 parts.
  • the ethylene propylene rubber (EPDM) ethylene propylene segment molar ratio is 60:40
  • the third monomer is ethylidene norbornene
  • the third monomer accounts for 3% by mass of the total mass of the three monomers.
  • the number average molecular weight is 150,000
  • the Mooney viscosity at 100 °C is 50 Pa's
  • the Shore A hardness is 40.
  • thermoplastic elastomer is an ethylene-propylene copolymer having a number average molecular weight of 150,000, a Mooney viscosity of 100 Pa s at 100 ° C, a Shore A hardness of 60, a melt index at 190 ° C and 2.16 kg. 1-5 g/10min
  • the polyethylene was a low density polyethylene having a number average molecular weight of 80,000 and a melt index of 5 g/10 min at 190 ° C and 2.16 kg.
  • the ethylene-vinyl acetate copolymer had a vinyl acetate content of 50% by weight and a melt index of 5 g/10 min at 190 ° C and 2.16 kg.
  • the compatibilizer was maleic anhydride grafted polyethylene with a graft ratio of 2%, a melt index of 2 g/10 min at 190 ° C and 2.16 kg.
  • the aluminum hydroxide is prepared by a Bayer-sintering combination method and modified by aminosilicone, and has a particle diameter D50 of 2 ⁇ m and a mesh number of 5,000 mesh.
  • the stabilizer is composed of the following components in parts by weight: calcium stearate: 40 parts, zinc stearate: 10 parts, tetra [ ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl) Propionate] pentaerythritol ester: 50 parts.
  • the silicone masterbatch is composed of the following components in parts by weight: low density polyethylene: 10 parts, siloxane: 50 parts, silica: 40 parts.
  • the low density polyethylene has a number average molecular weight of 50,000, a melt index of 5 g/10 min at 190 ° C and 2.16 kg.
  • the siloxane is methyl vinyl siloxane with a number average molecular weight of 800,000.
  • the silica was precipitated silica having a mesh size of 6,000 mesh.
  • the above 125 ° C irradiation cross-linked EPCV photovoltaic low-smoke halogen-free sheathed cable material preparation method comprises the following steps:
  • the wire is irradiated and crosslinked by an electron accelerator.
  • the components are melt blended by an internal mixer.
  • the specific parameters are: the mixing temperature is 160-175 ° C, and the mixing time is 15-25 minutes.
  • the single-screw extruder is divided into seven zones, and the operating temperatures of the zones are: 110-115 °C in the first zone, 115-120 °C in the second zone, and 115-120° in the third zone.
  • the fourth zone is 120-125 °C
  • the fifth zone is 120-125 °C
  • the sixth zone is 120-130 °C
  • the seventh zone is 125-130 °C.
  • the extruder is divided into four zones, and the working temperature of each zone is: the first zone is 150-160 ° C, The second zone is 165-175 ° C, the third zone is 165-175 ° C, and the fourth zone is 170-180 ° C.
  • a low-smoke halogen-free sheathed cable material for 125 ° C irradiation cross-linked EPCV photovoltaic mainly made of the following raw materials by weight: EPDM: 18 parts; thermoplastic elastomer (TPE) : 2 parts; Polyethylene: 5 parts; Ethylene-vinyl acetate copolymer: 12 parts; Compatibilizer: 2; Aluminium hydroxide 59 parts; Stabilizer: 2 parts; Silicone masterbatch: 2 parts.
  • the ethylene propylene rubber (EPDM) ethylene propylene segment molar ratio is 60:40
  • the third monomer is ethylidene borneene
  • the third monomer accounts for 3% by mass of the total mass of the three monomers.
  • the number average molecular weight is 150,000
  • the Mooney viscosity at 100 °C is 50 Pa's
  • the Shore A hardness is 40.
  • thermoplastic elastomer is an ethylene-propylene copolymer having a number average molecular weight of 150,000, a Mooney viscosity of 50 Pa's at 100 ° C, a Shore A hardness of 60, a melt index of 1 at 190 ° C and 2.16 kg. -5 g/10min.
  • the polyethylene is a low density polyethylene having a number average molecular weight of 80,000 and a melt index of 5 g/10 min at 190 ° C and 2.16 kg.
  • the ethylene-vinyl acetate copolymer had a vinyl acetate content of 50% by weight, and a melt index of 5 g/10 min at 190 ° C and 2.16 kg.
  • the compatibilizer is maleic anhydride grafted polyethylene with a graft ratio of 2%, a melting index of 2 g/10 min at 190 ° C and 2.16 kg.
  • the aluminum hydroxide is prepared by a Bayer-sintering combination method and modified by aminosilicone, and has a particle diameter D50 of 2 ⁇ m and a mesh number of 5,000 mesh.
  • the stabilizer is composed of - the following components in parts by weight: calcium stearate: 40 parts, zinc stearate: 10 parts, tetra [ ⁇ -(3,5-di-tert-butyl-4-hydroxybenzene) Propionate] pentaerythritol ester: 50 parts.
  • the silicone masterbatch is composed of the following components in parts by weight: low density polyethylene: 10 parts, siloxane: 50 parts, silica: 40 parts.
  • the low density polyethylene has a number average molecular weight of 50,000, 190 ° C and 2.16 kg.
  • the melt index below is 9 g/10 min.
  • the siloxane is methyl vinyl siloxane with a number average molecular weight of 800,000.
  • the silica is precipitated silica having a mesh number of 6,000 mesh.
  • the above 125 ° C irradiation cross-linked EPCV photovoltaic low-smoke halogen-free sheathed cable material preparation method comprises the following steps:
  • the wire is irradiated and crosslinked by an electron accelerator.
  • the components are melt blended by an internal mixer.
  • the specific parameters are: the mixing temperature is 160-175 ° C, and the mixing time is 15-25 minutes.
  • the single-screw extruder is divided into seven zones, and the operating temperatures of the zones are: 110-115 °C in the first zone, 115-120 °C in the second zone, and 115-120° in the third zone.
  • the fourth zone is 120-125 °C
  • the fifth zone is 120-125 °C
  • the sixth zone is 120-130 °C
  • the seventh zone is 125-130 °C.
  • the extruder is divided into four zones, and the working temperature of each zone is: first zone 150-160 °C, second zone 165-175 °C, third zone 165-175 °C, The fourth zone is 170-180 °C.
  • a low-smoke halogen-free sheathed cable material for 125 ° C irradiation cross-linked EPCV photovoltaic mainly made of the following raw materials by weight: EPDM: 16 parts; thermoplastic elastomer (TPE) : 1.5 parts; Polyethylene: 8 parts; Ethylene-vinyl acetate copolymer: 12 parts; Compatibilizer: 2.5; Aluminium hydroxide 56 parts; Stabilizer: 2 parts; Silicone masterbatch: 2 parts.
  • the ethylene propylene rubber (EPDM) ethylene propylene segment molar ratio is 60:40
  • the third monomer is ethylidene borneene
  • the third monomer accounts for 3% by mass of the total mass of the three monomers.
  • the number average molecular weight is 150,000
  • the Mooney viscosity at 100 °C is 50 Pa's
  • the Shore A hardness is 40.
  • thermoplastic elastomer is an ethylene-propylene copolymer having a number average molecular weight of 150,000, a Mooney viscosity of 50 Pa's at 100 ° C, a Shore A hardness of 60, a melt index of 1 at 190 ° C and 2.16 kg. -5 g/10min.
  • the polyethylene is a low density polyethylene having a number average molecular weight of 80,000 and a melt index of 5 g/10 min at 190 ° C and 2.16 kg.
  • the ethylene-vinyl acetate copolymer had a vinyl acetate content of 50% by weight, and a melt index of 5 g/10 min at 190 ° C and 2.16 kg.
  • the compatibilizer is maleic anhydride grafted polyethylene having a graft ratio of 2%, a melt index of 2 g/10 min at 190 ° C and 2.16 kg.
  • the aluminum hydroxide is prepared by a Bayer-sintering combination method and modified by aminosilicone, and has a particle diameter D50 of 2 ⁇ m and a mesh number of 5,000 mesh.
  • the stabilizer is composed of the following components in parts by weight: calcium stearate: 40 parts, zinc stearate: 10 parts, tetra [ ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl) Propionate] pentaerythritol ester: 50 parts.
  • the silicone masterbatch is composed of the following components in parts by weight: low density polyethylene: 10 parts, siloxane: 50 parts, silica: 40 parts.
  • the low density polyethylene has a number average molecular weight of 50,000, a melt index of 9 g/10 min at 190 ° C and 2.16 kg.
  • the siloxane is methyl vinyl siloxane with a number average molecular weight of 800,000.
  • the silica was precipitated silica having a mesh size of 6,000 mesh.
  • the above method for preparing 125 ° C radiation cross-linked EPCV photovoltaic low-smoke halogen-free sheathed cable material comprises the steps of:
  • the extruded particles are extruded through an extruder.
  • the wire is irradiated and crosslinked by an electron accelerator.
  • the components are melt blended by an internal mixer.
  • the specific parameters are: the mixing temperature is 160-175 ° C, and the mixing time is 15-25 minutes.
  • the single-screw extruder is divided into seven zones, and the operating temperatures of the zones are: 110-115 °C in the first zone, 115-120 °C in the second zone, and 115-120° in the third zone.
  • the fourth zone is 120-125 °C
  • the fifth zone is 120-125 °C
  • the sixth zone is 120-130 °C
  • the seventh zone is 125-130 °C.
  • the extruder is divided into four zones, and the working temperature of each zone is: first zone 150-160 °C, second zone 165-175 °C, third zone 165-175 °C, The fourth zone is 170-180 °C.
  • EPDM 10 parts
  • Polyethylene 25 parts
  • Compatibilizer 1 part
  • 45 parts of aluminum hydroxide 45 parts of aluminum hydroxide
  • stabilizer 1 part
  • silicone masterbatch 1 part.
  • the ethylene propylene rubber (EPDM) ethylene propylene segment molar ratio is 60:40
  • the third monomer is ethylidene borneene
  • the third monomer accounts for 1% by mass of the total mass of the three monomers.
  • the number average molecular weight is 50,000
  • the Mooney viscosity at 100 °C is 30 Pa's
  • the Shore A hardness is 20. .
  • the polyethylene is a low density polyethylene having a number average molecular weight of 50,000, a melt index of 3.6 g/10 min at 190 ° C and 2.16 kg.
  • the compatibilizing agent is maleic anhydride grafted polyethylene, and the graft ratio is 1%, and the melting index is 1 g/10 min at 190 ° C and 2.16 kg.
  • the aluminum hydroxide is prepared by a Bayer-sintering combination method, and is modified by aminosilicone, and has a particle diameter D50 of 1 ⁇ m and a mesh number of 4000 mesh.
  • the stabilizer is composed of the following components in parts by weight: calcium stearate: 35 parts, zinc stearate: 5 parts, tetra [ ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl) Propionate] pentaerythritol ester: 60 parts.
  • the silicone masterbatch consists of the following components in parts by weight: low density polyethylene: 10 parts, siloxane: 45 parts, silica: 15 parts.
  • the low density polyethylene has a number average molecular weight of 50,000, a melt index of 5 g/10 min at 190 ° C and 2.16 kg.
  • the siloxane is methyl vinyl siloxane with a number average molecular weight of 600,000.
  • the silica is precipitated silica having a mesh number of 5,000 mesh.
  • a low-smoke halogen-free sheathed cable material for 125 ° C irradiation cross-linked EPCV photovoltaic mainly made of the following raw materials by weight: EPDM: 20 parts; thermoplastic elastomer (TPE) : 5 parts; ethylene-vinyl acetate copolymer: 5 parts; compatibilizer: 5; 65 parts of aluminum hydroxide; stabilizer: 3 parts; silicone masterbatch: 3 parts.
  • the ethylene propylene rubber (EPDM) ethylene propylene segment molar ratio is 70:30
  • the third monomer is ethylidene norbornene
  • the third monomer accounts for 2% by mass of the total mass of the three monomers.
  • the number average molecular weight is 100,000
  • the Mooney viscosity at 100 ° C is 70 Pa-s
  • the Shore A hardness is 50.
  • thermoplastic elastomer is an ethylene-propylene copolymer having a number average molecular weight of 100,000, a Mooney viscosity of 100 Pa at 100 ° C, a Shore A hardness of 30, a melt index of 190 ° C and 2.16 kg. 4 g/10min.
  • the ethylene-vinyl acetate copolymer had a vinyl acetate content of 60% by weight, and a melt index of 5 g/10 min at 190 ° C and 2.16 kg.
  • the compatibilizing agent is a maleic anhydride grafted polyethylene having a graft ratio of 1.5%, a melt index of 3 g/10 min at 190 ° C and 2.16 kg.
  • the aluminum hydroxide is prepared by a Bayer-sintering combination method and modified by aminosilicone, and has a particle diameter D50 of 2 ⁇ m and a mesh size of 8000 mesh.
  • the stabilizer is composed of the following components in parts by weight: calcium stearate: 55 parts, zinc stearate: 35 Parts, tetrakis[ ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] pentaerythritol ester: 35 parts.
  • the silicone masterbatch is composed of the following components in parts by weight: Low density polyethylene: 20 parts, siloxane:
  • the low density polyethylene has a number average molecular weight of 100,000, a melt index of 10 g/10 min at 190 ° C and 2.16 kg.
  • the siloxane is methyl vinyl siloxane with a number average molecular weight of 1 million.
  • the silica is precipitated silica having a mesh number of 5,000 mesh.
  • a low-smoke halogen-free sheathed cable material for 125 ° C irradiation cross-linked EPCV photovoltaic mainly made of the following raw materials by weight: EPDM: 14 parts; thermoplastic elastomer (TPE) : 4 parts; Polyethylene: 10 parts; Ethylene-vinyl acetate copolymer: 8 parts; Compatibilizer: 2; 60 parts of aluminum hydroxide; Stabilizer: 2 parts; Silicone masterbatch: 2 parts.
  • the ethylene propylene rubber (EPDM) ethylene propylene segment molar ratio is 60:40
  • the third monomer is ethylidene borneene
  • the third monomer accounts for 2% by mass of the total mass of the three monomers.
  • the number average molecular weight is 100,000
  • the Mooney viscosity at 100 °C is 50 Pa's
  • the Shore A hardness is 40.
  • thermoplastic elastomer is an ethylene-propylene copolymer having a number average molecular weight of 150,000, a Mooney viscosity of 100 Pa-s at 100 ° C, a Shore A hardness of 50, melting at 190 ° C and 2.16 kg.
  • the index is 1-5 g/10 min.
  • the polyethylene was a low density polyethylene having a number average molecular weight of 80,000, and a melting index of 3 g/10 min at 190 ° C and 2.16 kg.
  • the ethylene-vinyl acetate copolymer had a vinyl acetate content of 50%, and a melt index of 4 g/10 min at 190 ° C and 2.16 kg.
  • the compatibilizer is maleic anhydride grafted polyethylene, and the graft ratio is 1.5%, 190 ° C and 2.16 kg.
  • the melt index is 2 g/10 min.
  • the aluminum hydroxide is prepared by a Bayer-sintering combination method and is modified by aminosilicone, and has a particle diameter D50 of 1 micrometer and a mesh number of 5,000 mesh.
  • the stabilizer is composed of the following components in parts by weight: calcium stearate: 40 parts, zinc stearate: 10 parts, tetra [ ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl) Propionate] pentaerythritol ester: 50 parts.
  • the silicone masterbatch is composed by weight of the following components: Low density polyethylene: 10 parts, siloxane: 50 parts, silica: 40 parts.
  • the low density polyethylene has a number average molecular weight of 80,000, a melt index of 8 g/10 min at 190 ° C and 2.16 kg.
  • the siloxane is methyl vinyl siloxane with a number average molecular weight of 800,000.
  • the silica was precipitated silica having a mesh number of 5,500 mesh.
  • a low-smoke halogen-free sheath cable material for 125 ° C irradiation cross-linked EPCV photovoltaic was prepared in the same manner as in Example 1.

Abstract

A zero halogen sheath material used for 125°C irradiation cross-linked EPCV photovoltaics, said material being made primarily of the following starting materials, in parts by weight: 10-20 parts of ethylene propylene diene monomer rubber; 0-5 parts of thermoplastic elastomer; 0-25 parts of polyethylene; 0-15 parts of ethylene-vinyl acetate copolymer; 1-5 parts of compatibilizer; 45-65 parts of aluminum hydroxide; 1-3 parts of stabilizer; 1-3 parts of silicone masterbatch. The product has excellent oil repellency properties and flame retardant properties, releases very little smoke during combustion, light transmittance in the smoke can reach more than 90%, and the product also has excellent mechanical properties and weather resistance properties, fully satisfying the performance requirements of UL 4703-2010 standards.

Description

一种 125'C辐照交联 EPCV光伏用无卤阻燃护套材料及其制备方法 技术领域  Halogen-free flame-retardant sheath material for 125°C irradiation cross-linking EPCV photovoltaic and preparation method thereof
本发明涉及一种低烟无卤电力电缆材料及其制备方法，具体涉及一种 125°C 辐照交联 EPCV光伏用低烟无卤阻燃护套材料及其制备方法。  The invention relates to a low-smoke halogen-free power cable material and a preparation method thereof, in particular to a 125°C radiation cross-linked EPCV photovoltaic low-smoke halogen-free flame-retardant sheath material and a preparation method thereof.
背景技术 Background technique
近年来， 随着能源危机的日益加剧以及人们环保意识的逐渐加强， 世界各 国纷纷制定发展新能源政策， 全球太阳能光伏产业得到了迅速发展。 根据我国 能源发展政策， 太阳能应用已列入重点发展能源之一， 国内光伏产业项目不断 推出， 呈现出欣欣向荣的光伏产业热。 在此背景下， 光伏电缆的用量也随之不 断增加， 进入稳定的市场成长期， 光伏电缆组件需求将保持高速发展。  In recent years, with the increasing energy crisis and the increasing awareness of environmental protection, countries around the world have formulated new energy policies, and the global solar photovoltaic industry has developed rapidly. According to China's energy development policy, solar energy application has been included in one of the key development energy sources. The domestic photovoltaic industry project has been continuously launched, showing a thriving photovoltaic industry fever. In this context, the amount of photovoltaic cable will continue to increase, and enter a stable market growth period, the demand for photovoltaic cable components will maintain rapid development.
光伏电线电缆作为光伏产业的重要组成部分， 其安全性和可靠性对于光伏 发电系统至关重要，而光伏线缆的安全性和可靠性则主要取决于光伏线缆材料。 目前在光伏线缆领域应用最广的是 XLPE类材料， XLPE类光伏线缆材料在应 用过程中存在着硬度大， 狭小空间内安装不便， 无法实现低烟无卤 VW-1 阻燃 级别等不足之处。  As an important part of the photovoltaic industry, photovoltaic wire and cable, its safety and reliability are crucial for photovoltaic power generation systems, and the safety and reliability of photovoltaic cables are mainly determined by photovoltaic cable materials. At present, the most widely used in the field of photovoltaic cables is XLPE materials. XLPE-type photovoltaic cable materials have high hardness in the application process, inconvenient installation in a small space, and can not achieve low flame-free halogen-free VW-1 flame retardant level. Where.
EPCV是一种橡胶和塑料的共混物， 具有橡胶优异的弹性和高填充性以及 塑料出色的力学性能和加工性能。 其应用于光伏线缆， 不仅具有优异的力学性 能和电气性能， 而且具有极佳的阻燃性能和优异的防油性能， 可实现无卤阻燃 VW-1级别， 不含磷氮系阻燃剂， 在燃烧过程中烟释放量极低， 真正做到绿色环 保。 因此， 125°CEPCV光伏用低烟无卤护套材料具有非常好的经济效益和社会 效益。  EPCV is a blend of rubber and plastic with excellent rubber elasticity and high filling properties as well as excellent mechanical and processing properties of plastics. It is applied to photovoltaic cables, which not only has excellent mechanical and electrical properties, but also has excellent flame retardant properties and excellent oil-repellent properties. It can achieve halogen-free flame retardant VW-1 grade, and does not contain phosphorus-nitrogen flame retardant. The amount of smoke released during the combustion process is extremely low, and it is truly green. Therefore, the 125° CEPCV photovoltaic low-smoke halogen-free sheath material has very good economic and social benefits.
CN102766293A 公开了一种辐照交联低烟无卤无红磷阻燃材料， 包括： 乙 烯 -乙酸乙烯酯共聚物 10-80重量份； 乙烯-辛烯共聚物和 /或乙烯-丁烯共聚物和 / 或三元乙丙橡胶 5-30重量份；聚乙烯 0-100重量份；聚合物相容剂 1-20重量份； 有机硅聚合物 0.5-10重量份；复合抗氧剂 1-10重量份；氢氧化铝和 /或氢氧化镁 和 /或改性氢氧化铝和 /或改性氢氧化镁 0-200重量份;高分子量聚磷酸铵 0.1-100 重量份和 /或磷酸酯类阻燃剂 0.1-50重量份和 /或三聚氰胺氰脲酸盐 0.1-50重量 份， 应用于热缩套管阻燃等级达到美国 UL224VW-1 标准， 应用于电线电缆达 到美国 UL1581VW-1标准， 且不含卤素及红磷， 对环境友好。 CN102766293A discloses an irradiation cross-linked low-smoke halogen-free and non-red phosphorus flame retardant material, including: 10 to 80 parts by weight of an ene-vinyl acetate copolymer; 5 to 30 parts by weight of an ethylene-octene copolymer and/or an ethylene-butene copolymer and/or an ethylene propylene diene rubber; 0 to 100 parts by weight of a polyethylene; 1-20 parts by weight of the polymer compatibilizer; 0.5-10 parts by weight of the silicone polymer; 1-10 parts by weight of the composite antioxidant; aluminum hydroxide and/or magnesium hydroxide and/or modified aluminum hydroxide and/or Or modified magnesium hydroxide 0-200 parts by weight; high molecular weight ammonium polyphosphate 0.1-100 parts by weight and / or phosphate flame retardant 0.1-50 parts by weight and / or melamine cyanurate 0.1-50 parts by weight, It is applied to the heat-shrinkable sleeve to meet the UL224VW-1 standard of the United States. It is applied to the wire and cable to meet the UL1581VW-1 standard of the United States, and is halogen-free and red phosphorus-free. It is environmentally friendly.
发明内容 Summary of the invention
针对现有技术中的问题，本发明的目的在于提供一种 125 °C辐照交联 EPCV 光伏用无卤阻燃护套材料， 所述无卤阻燃护套材料具有优异的防油性能和阻燃 性能， 燃烧时烟释放量极低， 烟中透光率高， 同时具有优异的力学性能和电气 性能。  In view of the problems in the prior art, an object of the present invention is to provide a halogen-free flame-retardant sheath material for 125 ° C irradiation cross-linked EPCV photovoltaic, which has excellent oil-proof performance and Flame retardant performance, extremely low smoke emission during combustion, high light transmittance in smoke, and excellent mechanical and electrical properties.
为了实现上述目的， 本发明采用了如下技术方案：  In order to achieve the above object, the present invention adopts the following technical solutions:
一种 125°C辐照交联 EPCV光伏用无卤阻燃护套材料， 其按重量份数主要 由以下原料制成：  A 125 ° C irradiation cross-linked EPCV photovoltaic halogen-free flame-retardant sheath material, which is mainly made up of the following raw materials by weight:
三元乙丙橡胶 10〜20份  EPDM rubber 10~20 parts
热塑性弹性体 0〜5份  Thermoplastic elastomer 0~5 parts
聚乙烯 0〜25份  Polyethylene 0~25 parts
乙烯-醋酸乙烯共聚物 0〜15份  Ethylene-vinyl acetate copolymer 0~15 parts
相容剂 1〜5份  Compatibilizer 1~5 parts
氢氧化铝 45-65份  Aluminum hydroxide 45-65 parts
安定剂 1〜3份  Stabilizer 1~3 parts
硅酮母粒 1〜3份。 所述三元乙丙橡胶的重量份数例如为 11份、 12份、 13份、 14份、 15份、 16份、 17份、 18份或 19份。 1 to 3 parts of silicone masterbatch. The parts by weight of the ethylene propylene diene monomer are, for example, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts or 19 parts.
所述热塑性弹性体 （TPE) 的重量份数例如为 0.5份、 1份、 1.5份、 2份、 2.5份、 3份、 3.5份、 4份或 4.5份。  The thermoplastic elastomer (TPE) is, for example, 0.5 parts by weight, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts or 4.5 parts by weight.
所述聚乙烯的重量份数例如为 1份、 3份、 5份、 7份、 9份、 11份、 13份、 15份、 17份、 19份、 21份或 23份。  The parts by weight of the polyethylene are, for example, 1 part, 3 parts, 5 parts, 7 parts, 9 parts, 11 parts, 13 parts, 15 parts, 17 parts, 19 parts, 21 parts or 23 parts.
所述乙烯-醋酸乙烯共聚物的重量份数例如为 0.5份、 1份、 2份、 3份、 4 份、 5份、 6份、 7份、 8份或 9份。  The parts by weight of the ethylene-vinyl acetate copolymer are, for example, 0.5 part, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts or 9 parts.
所述相容剂的重量份数例如为 1.5份、 2份、 2.5份、 3份、 3.5份、 4份或 4.5份。  The parts by weight of the compatibilizer are, for example, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts or 4.5 parts.
所述氢氧化铝的重量份数例如为 47份、 49份、 51份、 52份、 54份、 57 份、 60份或 63份。  The parts by weight of the aluminum hydroxide are, for example, 47 parts, 49 parts, 51 parts, 52 parts, 54 parts, 57 parts, 60 parts or 63 parts.
所述安定剂的重量份数例如为 1.2份、 1.5份、 1.8份、 2.1份、 2.4份、 2.7 份或 2.9份。  The stabilizer is, for example, 1.2 parts, 1.5 parts, 1.8 parts, 2.1 parts, 2.4 parts, 2.7 parts or 2.9 parts by weight.
所述硅酮母粒的重量份数例如为 1.2份、 1.5份、 1.8份、 2.1份、 2.4份、 2.7份或 2.9份。  The parts by weight of the silicone master batch are, for example, 1.2 parts, 1.5 parts, 1.8 parts, 2.1 parts, 2.4 parts, 2.7 parts or 2.9 parts.
优选地， 一种 125°C辐照交联 EPCV光伏用无卤阻燃护套材料， 其按重量 份数主要由以下原料制成：  Preferably, a 125 ° C radiation crosslinked EPCV photovoltaic halogen-free flame-retardant sheath material is mainly made up of the following raw materials by weight:
三元乙丙橡胶 10.5〜18.5份  EPDM rubber 10.5~18.5 parts
热塑性弹性体 0.5〜5份  Thermoplastic elastomer 0.5~5 parts
聚乙烯 0.5〜25份  Polyethylene 0.5~25 parts
乙烯-醋酸乙烯共聚物 0.5〜15份  Ethylene-vinyl acetate copolymer 0.5~15 parts
相容剂 1〜5份 安定剂Compatibilizer 1~5 parts Stabilizer
Figure imgf000005_0001
Figure imgf000005_0001
优选地， 一种 125°C辐照交联 EPCV光伏用无卤阻燃护套材料， 其按重] 份数主要由以下原料制成:  Preferably, a 125 ° C irradiation cross-linked EPCV photovoltaic halogen-free flame-retardant sheath material, the weight of which is mainly made of the following materials:
三元乙丙橡胶 11〜18份  EPDM rubber 11~18 parts
热塑性弹性体 1〜5份  Thermoplastic elastomer 1~5 parts
2-23份  2-23 servings
乙烯-醋酸乙烯共聚物 2〜15份  Ethylene-vinyl acetate copolymer 2~15 parts
相容剂 1〜5份  Compatibilizer 1~5 parts
50-60份  50-60 servings
安定剂 1〜3份  Stabilizer 1~3 parts
1〜3份。  1 to 3 servings.
上述 125°C辐照交联 EPCV光伏用无卤阻燃护套材料可由配方量的原料经 常规的密炼机共混造粒， 挤出机挤出造粒制得。  The above-mentioned 125 ° C irradiation cross-linked EPCV photovoltaic halogen-free flame-retardant sheath material can be obtained by blending and granulating a predetermined amount of raw materials through a conventional internal mixer and extruding and granulating the extruder.
优选地， 所述三元乙丙橡胶（EPDM)乙烯丙烯链段摩尔比为 60:40〜70:30， 第三单体为乙叉冰片烯， 第三单体占三种单体的总质量的质量百分比为 1〜3%， 数均分子量为 5〜15万， 100°C门尼粘度为 30〜70 Pa s, 邵氏 A硬度为 20〜50。  Preferably, the ethylene propylene rubber (EPDM) ethylene propylene segment molar ratio is 60:40~70:30, the third monomer is ethylidene borneene, and the third monomer accounts for the total mass of the three monomers. The mass percentage is 1 to 3%, the number average molecular weight is 5 to 150,000, the Mooney viscosity at 100 ° C is 30 to 70 Pa s, and the Shore A hardness is 20 to 50.
优选地， 所述热塑性弹性体 （TPE) 为乙烯-丙烯共聚物， 其数均分子量为 10〜20万， 100°C门尼粘度为 30〜60 Pa-s， 邵氏 A硬度为 30〜60， 190°C和 2.16kg 下的熔融指数为 1〜5 g/10min。  Preferably, the thermoplastic elastomer (TPE) is an ethylene-propylene copolymer having a number average molecular weight of 10 to 200,000, a Mooney viscosity of 100 to 60 Pa-s at 100 ° C, and a Shore A hardness of 30 to 60. The melt index at 190 ° C and 2.16 kg is 1 to 5 g/10 min.
优选地，所述聚乙烯为低密度聚乙烯，数均分子量 5〜15万， 190°C和 2.16kg 下的熔融指数为 1〜5 g/10min。 优选地， 所述乙烯-醋酸乙烯共聚物的醋酸乙烯含量为 40〜60wt%， 190°C和 2.16kg下的熔融指数为 3〜5 g/10min。 Preferably, the polyethylene is a low density polyethylene having a number average molecular weight of 5 to 150,000, and a melt index of 1 to 5 g/10 min at 190 ° C and 2.16 kg. Preferably, the ethylene-vinyl acetate copolymer has a vinyl acetate content of 40 to 60% by weight, and a melt index of 3 to 5 g/10 min at 190 ° C and 2.16 kg.
优选地， 所述相容剂为马来酸酐接枝聚乙烯， 接枝率为 1〜2%， 190°C和 2.16kg下的熔融指数为 1〜3 g/10min。  Preferably, the compatibilizing agent is maleic anhydride grafted polyethylene, the graft ratio is 1 to 2%, and the melt index at 190 ° C and 2.16 kg is 1 to 3 g/10 min.
优选地， 所述氢氧化铝为拜耳 -烧结联合法制备。 优选地， 所述氢氧化铝采 用氨基硅垸进行改性， 其粒径 D50为 1〜2微米， 目数 4000〜8000目。  Preferably, the aluminum hydroxide is prepared by a Bayer-sintering combination process. Preferably, the aluminum hydroxide is modified with aminosilicone, and has a particle diameter D50 of 1 to 2 μm and a mesh number of 4000 to 8000 mesh.
优选地， 所述安定剂由下述组分按重量份组成： 硬脂酸钙 35〜55份， 硬脂 酸锌 5〜35份， 四 [β-(3,5-二叔丁基 -4-羟基苯基)丙酸酯]季戊四醇酯 35〜60份。  Preferably, the stabilizer is composed of the following components in parts by weight: 35 to 55 parts of calcium stearate, 5 to 35 parts of zinc stearate, and four [β-(3,5-di-tert-butyl-4) -Hydroxyphenyl)propionate] pentaerythritol ester 35 to 60 parts.
优选地， 所述硅酮母粒由下述组分按重量份组成： 10〜20份低密度聚乙烯， 45〜75份硅氧垸， 15〜55份二氧化硅。  Preferably, the silicone masterbatch is composed of the following components in parts by weight: 10 to 20 parts of low density polyethylene, 45 to 75 parts of siloxane, 15 to 55 parts of silica.
优选地， 所述低密度聚乙烯数均分子量 5〜10万， 190°C和 2.16kg下的熔融 指数 5〜10 g/10min。  Preferably, the low-density polyethylene has a number average molecular weight of 5 to 100,000, and a melt index of 5 to 10 g/10 min at 190 ° C and 2.16 kg.
优选地， 所述硅氧垸为甲基乙烯基硅氧垸， 数均分子量 60〜100万。  Preferably, the siloxane is methyl vinyl siloxane, and the number average molecular weight is from 60 to 1,000,000.
优选地， 所述二氧化硅为沉淀法二氧化硅， 目数 5000〜6000目。  Preferably, the silica is precipitated silica having a mesh number of 5000 to 6000 mesh.
本发明的目的之二在于提供一种如上所述的 125°C辐照交联 EPCV光伏用 低烟无卤阻燃护套材料的制备方法， 经密炼机共混造粒， 挤出机挤出造粒， 即 可制得本发明的 125°C辐照交联 EPCV光伏用低烟无卤阻燃护套材料。  The second object of the present invention is to provide a method for preparing a 125 ° C irradiation crosslinked EPCV photovoltaic low-smoke halogen-free flame-retardant sheath material as described above, which is blended and granulated by an internal mixer, and extruded by an extruder. After granulation, the 125 ° C irradiation crosslinked EPCV photovoltaic low-smoke halogen-free flame-retardant sheath material of the present invention can be obtained.
一种如上所述的 125°C辐照交联 EPCV光伏用低烟无卤阻燃护套材料的制 备方法， 所述方法包括如下步骤：  A method for preparing a 125 ° C irradiation cross-linked EPCV photovoltaic low-smoke halogen-free flame-retardant sheath material as described above, the method comprising the steps of:
( 1 )将配方量的各组分通过密炼机熔融共混，然后通过单螺杆挤出机造粒; (1) the components of the formula amount are melt-blended by an internal mixer, and then granulated by a single-screw extruder;
(2) 将步骤 （1 ) 得到的粒子通过挤出机挤出线材； (2) extruding the particles obtained in step (1) through an extruder;
(3 )线材经过电子加速器进行辐照交联， 得到 125 °C辐照交联 EPCV光伏 用低烟无卤阻燃护套材料。 优选地， 步骤 （1) 的密炼温度为 160〜175°C， 密炼时间为 15〜25分钟。 所述密炼温度例如为 162 °C、 164 °C、 166°C、 168°C、 170 °C、 172 °C或 174 °C 所述密炼时间例如为 16分钟、 17分钟、 18分钟、 19分钟、 20分钟、 2 分钟、 22分钟、 23分钟或 24分钟。 (3) The wire was irradiated and crosslinked by an electron accelerator to obtain a low-smoke halogen-free flame-retardant sheath material for 125 °C irradiation cross-linked EPCV photovoltaic. Preferably, the mixing temperature of the step (1) is 160 to 175 ° C, and the mixing time is 15 to 25 minutes. The mixing temperature is, for example, 162 ° C, 164 ° C, 166 ° C, 168 ° C, 170 ° C, 172 ° C or 174 ° C. The mixing time is, for example, 16 minutes, 17 minutes, 18 minutes, 19 minutes, 20 minutes, 2 minutes, 22 minutes, 23 minutes or 24 minutes.
优选地， 步骤（1)所述单螺杆挤出机分为七个区， 各区的工作温度为： 一区 110〜115°C， 第二区 115〜120°C， 第三区 115〜120°C， 第四区 120〜125°C， 第五区 120〜125°C， 第六区 120〜130°C， 第七区 125〜130°C。  Preferably, the single-screw extruder of the step (1) is divided into seven zones, and the working temperature of each zone is: one zone 110~115°C, the second zone 115~120°C, the third zone 115~120° C, the fourth zone is 120 to 125 ° C, the fifth zone is 120 to 125 ° C, the sixth zone is 120 to 130 ° C, and the seventh zone is 125 to 130 ° C.
所述第一区的温度例如为 110.5°C、 lire, 111.5°C、 112°C、 112.5°C、 113°C 113.5°C、 114°C或 114.5°Co  The temperature of the first zone is, for example, 110.5 ° C, lire, 111.5 ° C, 112 ° C, 112.5 ° C, 113 ° C 113.5 ° C, 114 ° C or 114.5 ° Co.
所述第二区的温度例如为 115.5°C、 116°C、 116.5°C、 117°C、 117.5°C、 118°C 118.5°C、 119°C或 119.5°C。  The temperature of the second zone is, for example, 115.5 ° C, 116 ° C, 116.5 ° C, 117 ° C, 117.5 ° C, 118 ° C 118.5 ° C, 119 ° C or 119.5 ° C.
所述第三区的温度例如为 115.5°C、 116°C、 116.5°C、 117°C、 117.5°C、 118°C 118.5°C、 119°C或 119.5°C。  The temperature of the third zone is, for example, 115.5 ° C, 116 ° C, 116.5 ° C, 117 ° C, 117.5 ° C, 118 ° C 118.5 ° C, 119 ° C or 119.5 ° C.
所述第四区的温度例如为 120.5°C、 121°C、 121.5°C、 122°C、 122.5°C、 123 °C 123.5°C、 124 °C或 124.5°C。  The temperature of the fourth zone is, for example, 120.5 ° C, 121 ° C, 121.5 ° C, 122 ° C, 122.5 ° C, 123 ° C 123.5 ° C, 124 ° C or 124.5 ° C.
所述第五区的温度例如为 120.5°C、 121°C、 121.5°C、 122°C、 122.5°C、 123 °C 123.5°C、 124 °C或 124.5°C。  The temperature of the fifth zone is, for example, 120.5 ° C, 121 ° C, 121.5 ° C, 122 ° C, 122.5 ° C, 123 ° C 123.5 ° C, 124 ° C or 124.5 ° C.
所述第六区的温度例如为 121°C、 122°C、 123°C、 124°C、 125°C、 126°C、 127°C、 128°C或 129°C。  The temperature of the sixth zone is, for example, 121 ° C, 122 ° C, 123 ° C, 124 ° C, 125 ° C, 126 ° C, 127 ° C, 128 ° C or 129 ° C.
所述第七区的温度例如为 125.5°C、 126°C、 126.5°C、 127°C、 127.5°C、 128°C 128.5°C、 129°C或 129.5°C。  The temperature of the seventh zone is, for example, 125.5 ° C, 126 ° C, 126.5 ° C, 127 ° C, 127.5 ° C, 128 ° C 128.5 ° C, 129 ° C or 129.5 ° C.
优选地， 步骤（2) 中所述挤出机分为四个区， 各区的工作温度为： 第一 Preferably, the extruder in the step (2) is divided into four zones, and the operating temperature of each zone is:
150-160 °C, 第二区 165〜175°C， 第三区 165〜175°C， 第四区 170〜180°C。 所述第一区的温度例如为 151 °C、 152°C、 153 °C、 154°C、 155°C、 156°C、 157°C、 158°C或 159°C。 150-160 ° C, the second zone is 165 to 175 ° C, the third zone is 165 to 175 ° C, and the fourth zone is 170 to 180 ° C. The temperature of the first zone is, for example, 151 ° C, 152 ° C, 153 ° C, 154 ° C, 155 ° C, 156 ° C, 157 ° C, 158 ° C or 159 ° C.
所述第二区的温度例如 166°C、 167°C、 168°C、 169°C、 170°C、 171 °C、 172°C、 173 °C或 174 °C。  The temperature of the second zone is, for example, 166 ° C, 167 ° C, 168 ° C, 169 ° C, 170 ° C, 171 ° C, 172 ° C, 173 ° C or 174 ° C.
所述第三区的温度例如为 166°C、 167°C、 168°C、 169°C、 170°C、 171 °C、 172 °C、 173 °C或 174°C。  The temperature of the third zone is, for example, 166 ° C, 167 ° C, 168 ° C, 169 ° C, 170 ° C, 171 ° C, 172 ° C, 173 ° C or 174 ° C.
所述第四区的温度例如为 171 °C、 172°C、 173 °C、 174°C、 175°C、 176°C、 177°C、 178°C或 179°C。  The temperature of the fourth zone is, for example, 171 ° C, 172 ° C, 173 ° C, 174 ° C, 175 ° C, 176 ° C, 177 ° C, 178 ° C or 179 ° C.
与已有技术相比， 本发明具有如下有益效果：  Compared with the prior art, the present invention has the following beneficial effects:
本发明的产品具有优异的阻燃性能和防油性能，可实现无卤阻燃 VW-1 , 以 及可通过 UL44中的防油要求。  The product of the present invention has excellent flame retardancy and oil repellency, can achieve halogen-free flame retardant VW-1, and can pass the oil-proof requirements of UL44.
本发明的产品燃烧时烟释放量极低， 烟中透光率可达到 90%以上， 同时具 有优良的力学性能和耐气候性， 完全满足 UL4703-2010标准性能要求。  The product of the invention has very low smoke emission during combustion, and the light transmittance in the smoke can reach more than 90%, and has excellent mechanical properties and weather resistance, and fully meets the performance requirements of the UL4703-2010 standard.
具体实 J ^r式 Concrete J ^r
下面通过具体实施方式来进一步说明本发明的技术方案。  The technical solution of the present invention will be further described below by way of specific embodiments.
实施例 1  Example 1
一种 125°C辐照交联 EPCV光伏用低烟无卤护套电缆材料， 按重量份数主 要由以下原料制成： 三元乙丙橡胶 （EPDM) : 15份； 热塑性弹性体 （TPE): 1 份； 聚乙烯： 5份； 乙烯 -醋酸乙烯共聚物： 10份； 相容剂： 2; 氢氧化铝 63份; 安定剂： 2份； 硅酮母粒： 2份。  A low-smoke halogen-free sheathed cable material for 125 ° C irradiation cross-linked EPCV photovoltaic, mainly made of the following raw materials by weight: EPDM: 15 parts; thermoplastic elastomer (TPE) : 1 part; Polyethylene: 5 parts; Ethylene-vinyl acetate copolymer: 10 parts; Compatibilizer: 2; 63 parts of aluminum hydroxide; Stabilizer: 2 parts; Silicone masterbatch: 2 parts.
所述三元乙丙橡胶 （EPDM) 乙烯丙烯链段摩尔比为 60:40， 第三单体为乙 叉冰片烯， 第三单体占三种单体的总质量的质量百分比为 3%， 数均分子量为 15万， 100 °C门尼粘度为 50 Pa's, 邵氏 A硬度为 40。 所述热塑性弹性体（TPE)为乙烯〜丙烯共聚物，其数均分子量 15万， 100°C 门尼粘度为 50 Pa s, 邵氏 A硬度为 60， 190°C和 2.16kg下的熔融指数为 1〜5 g/10min。 The ethylene propylene rubber (EPDM) ethylene propylene segment molar ratio is 60:40, the third monomer is ethylidene norbornene, and the third monomer accounts for 3% by mass of the total mass of the three monomers. The number average molecular weight is 150,000, the Mooney viscosity at 100 °C is 50 Pa's, and the Shore A hardness is 40. The thermoplastic elastomer (TPE) is an ethylene-propylene copolymer having a number average molecular weight of 150,000, a Mooney viscosity at 100 ° C of 50 Pa s, a Shore A hardness of 60, a melt index at 190 ° C and 2.16 kg. It is 1~5 g/10min.
所述聚乙烯为低密度聚乙烯， 数均分子量 8万， 190°C和 2.16kg下熔融指 数为 5 g/10mino  The polyethylene is a low density polyethylene having a number average molecular weight of 80,000, a melting index of 5 g/10 mino at 190 ° C and 2.16 kg.
所述乙烯-醋酸乙烯共聚物的醋酸乙烯含量为 50wt%， 190°C和 2.16kg下熔 融指数为 5 g/10min。  The ethylene-vinyl acetate copolymer had a vinyl acetate content of 50% by weight, and a melting index of 5 g/10 min at 190 ° C and 2.16 kg.
所述相容剂为马来酸酐接枝聚乙烯， 接枝率为 2%， 190°C和 2.16kg下熔融 指数为 2 g/10min。  The compatibilizer was maleic anhydride grafted polyethylene having a graft ratio of 2%, a melt index of 2 g/10 min at 190 ° C and 2.16 kg.
所述氢氧化铝为拜耳-烧结联合法制备的， 采用氨基硅垸进行改性， 其粒径 D50为 2微米， 目数 5000目。  The aluminum hydroxide is prepared by a Bayer-sintering combination method and is modified by aminosilicone, and has a particle diameter D50 of 2 μm and a mesh number of 5,000 mesh.
所述安定剂由下述组分按重量份组成：硬脂酸钙： 40份，硬脂酸锌： 10份， 四 [β-(3,5-二叔丁基 -4-羟基苯基)丙酸酯]季戊四醇酯： 50份。  The stabilizer is composed of the following components in parts by weight: calcium stearate: 40 parts, zinc stearate: 10 parts, tetra [β-(3,5-di-tert-butyl-4-hydroxyphenyl) Propionate] pentaerythritol ester: 50 parts.
所述硅酮母粒由下述组分按重量份组成： 低密度聚乙烯： 10份， 硅氧垸： 50份， 二氧化硅： 40份。 所述低密度聚乙烯数均分子量 5万， 190°C和 2.16kg 下的熔融指数 5g/10min。所述的硅氧垸为甲基乙烯基硅氧垸，数均分子量 80万。 所述二氧化硅为沉淀法二氧化硅， 目数 6000目。  The silicone masterbatch is composed by weight of the following components: Low density polyethylene: 10 parts, siloxane: 50 parts, silica: 40 parts. The low density polyethylene has a number average molecular weight of 50,000, a melt index of 5 g/10 min at 190 ° C and 2.16 kg. The siloxane is methyl vinyl siloxane with a number average molecular weight of 800,000. The silica was precipitated silica having a mesh number of 6,000 mesh.
上述 125°C辐照交联 EPCV光伏用低烟无卤护套电缆材料制备方法包括步 骤：  The above method for preparing 125 ° C radiation cross-linked EPCV photovoltaic low-smoke halogen-free sheathed cable material comprises the steps of:
( 1 ) 准确称量配方各组分；  (1) accurately weigh the components of the formula;
(2 ) 将称量好的原料通过密炼机熔融共混然后依次通过单螺杆挤出机造 粒；  (2) The weighed raw materials are melt blended through an internal mixer and then sequentially granulated by a single screw extruder;
(3 ) 将造好的粒子通过挤出机挤出线材。 (4) 线材经过电子加速器进行辐照交联。 (3) The extruded particles are extruded through an extruder. (4) The wire is irradiated and crosslinked by an electron accelerator.
将各组分通过密炼机熔融共混， 具体参数为： 密炼温度为 160-175°C， 密炼 时间为 15-25分钟。  The components are melt blended by an internal mixer. The specific parameters are: the mixing temperature is 160-175 ° C, and the mixing time is 15-25 minutes.
所述步骤（2) 中， 单螺杆挤出机分为七个区， 各区的工作温度为： 第一区 110-115°C , 第二区 115-120°C， 第三区 115-120°C， 第四区 120-125 °C , 第五区 120-125°C , 第六区 120-130°C， 第七区 125-130°C  In the step (2), the single-screw extruder is divided into seven zones, and the operating temperatures of the zones are: 110-115 ° C in the first zone, 115-120 ° C in the second zone, and 115-120 ° in the third zone. C, the fourth zone is 120-125 °C, the fifth zone is 120-125 °C, the sixth zone is 120-130 °C, and the seventh zone is 125-130 °C.
所述步骤 (3 )中，挤出机分为四个区，各区的工作温度为：第一区 150-160 °C， 第二区 165-175°C， 第三区 165-175°C， 第四区 170-180°C。  In the step (3), the extruder is divided into four zones, and the operating temperatures of the zones are: 150-160 ° C in the first zone, 165-175 ° C in the second zone, and 165-175 ° C in the third zone. The fourth zone is 170-180 °C.
实施例 2  Example 2
一种 125°C辐照交联 EPCV光伏用低烟无卤护套电缆材料， 按重量份数主 要由以下原料制成： 三元乙丙橡胶 （EPDM): 12份； 热塑性弹性体 （TPE): 2 份； 聚乙烯： 10份； 乙烯 -醋酸乙烯共聚物： 10份； 相容剂： 2; 氢氧化铝 60 份； 安定剂： 2份； 硅酮母粒： 2份。  A 125 ° C irradiation cross-linked EPCV photovoltaic low-smoke halogen-free sheathed cable material, mainly made up of the following raw materials by weight: EPDM: 12 parts; thermoplastic elastomer (TPE) : 2 parts; Polyethylene: 10 parts; Ethylene-vinyl acetate copolymer: 10 parts; Compatibilizer: 2; 60 parts of aluminum hydroxide; Stabilizer: 2 parts; Silicone masterbatch: 2 parts.
所述三元乙丙橡胶（EPDM) 乙烯丙烯链段摩尔比为 60:40， 第三单体为乙 叉冰片烯， 第三单体占三种单体的总质量的质量百分比为 3%， 数均分子量为 15万， 100 °C门尼粘度为 50 Pa's, 邵氏 A硬度为 40。  The ethylene propylene rubber (EPDM) ethylene propylene segment molar ratio is 60:40, the third monomer is ethylidene norbornene, and the third monomer accounts for 3% by mass of the total mass of the three monomers. The number average molecular weight is 150,000, the Mooney viscosity at 100 °C is 50 Pa's, and the Shore A hardness is 40.
所述的热塑性弹性体（TPE)为乙烯-丙烯共聚物，数均分子量 15万， 100°C 门尼粘度为 50 Pa s, 邵氏 A硬度为 60， 190°C和 2.16kg下的熔融指数为 1-5 g/10min  The thermoplastic elastomer (TPE) is an ethylene-propylene copolymer having a number average molecular weight of 150,000, a Mooney viscosity of 100 Pa s at 100 ° C, a Shore A hardness of 60, a melt index at 190 ° C and 2.16 kg. 1-5 g/10min
所述聚乙烯为低密度聚乙烯， 数均分子量 8万， 190°C和 2.16kg下的熔融 指数为 5 g/10min。  The polyethylene was a low density polyethylene having a number average molecular weight of 80,000 and a melt index of 5 g/10 min at 190 ° C and 2.16 kg.
所述的乙烯-醋酸乙烯共聚物的醋酸乙烯含量为 50wt%， 190°C和 2.16kg下 的熔融指数为 5 g/10min。 所述相容剂为马来酸酐接枝聚乙烯， 接枝率为 2%， 190°C和 2.16kg下熔融 指数为 2 g/10min。 The ethylene-vinyl acetate copolymer had a vinyl acetate content of 50% by weight and a melt index of 5 g/10 min at 190 ° C and 2.16 kg. The compatibilizer was maleic anhydride grafted polyethylene with a graft ratio of 2%, a melt index of 2 g/10 min at 190 ° C and 2.16 kg.
所述的氢氧化铝为拜耳-烧结联合法制备的， 采用氨基硅垸进行改性， 其粒 径 D50为 2微米， 目数 5000目。  The aluminum hydroxide is prepared by a Bayer-sintering combination method and modified by aminosilicone, and has a particle diameter D50 of 2 μm and a mesh number of 5,000 mesh.
所述的安定剂由下述组分按重量份组成： 硬脂酸钙： 40份， 硬脂酸锌： 10 份， 四 [β-(3,5-二叔丁基 -4-羟基苯基)丙酸酯]季戊四醇酯： 50份。  The stabilizer is composed of the following components in parts by weight: calcium stearate: 40 parts, zinc stearate: 10 parts, tetra [β-(3,5-di-tert-butyl-4-hydroxyphenyl) Propionate] pentaerythritol ester: 50 parts.
所述的硅酮母粒由下述组分按重量份组成： 低密度聚乙烯： 10份， 硅氧垸： 50份， 二氧化硅： 40份。所述的低密度聚乙烯数均分子量 5万， 190°C和 2.16kg 下的熔融指数 5 g/10min。 所述的硅氧垸为甲基乙烯基硅氧垸， 数均分子量 80 万。 所述的二氧化硅为沉淀法二氧化硅， 目数 6000目。  The silicone masterbatch is composed of the following components in parts by weight: low density polyethylene: 10 parts, siloxane: 50 parts, silica: 40 parts. The low density polyethylene has a number average molecular weight of 50,000, a melt index of 5 g/10 min at 190 ° C and 2.16 kg. The siloxane is methyl vinyl siloxane with a number average molecular weight of 800,000. The silica was precipitated silica having a mesh size of 6,000 mesh.
上述 125°C辐照交联 EPCV光伏用低烟无卤护套电缆材料制备方法包括如 下步骤：  The above 125 ° C irradiation cross-linked EPCV photovoltaic low-smoke halogen-free sheathed cable material preparation method comprises the following steps:
( 1 ) 准确称量配方各组分；  (1) accurately weigh the components of the formula;
(2 ) 将称量好的原料通过密炼机熔融共混然后依次通过单螺杆挤出机造 粒；  (2) The weighed raw materials are melt blended through an internal mixer and then sequentially granulated by a single screw extruder;
(3 ) 将造好的粒子通过挤出机挤出线材。  (3) The extruded particles are extruded through an extruder.
(4 ) 线材经过电子加速器进行辐照交联。  (4) The wire is irradiated and crosslinked by an electron accelerator.
将各组分通过密炼机熔融共混， 具体参数为： 密炼温度为 160-175°C， 密炼 时间为 15-25分钟。  The components are melt blended by an internal mixer. The specific parameters are: the mixing temperature is 160-175 ° C, and the mixing time is 15-25 minutes.
所述步骤（2 ) 中， 单螺杆挤出机分为七个区， 各区的工作温度为： 第一区 110-115 °C , 第二区 115-120°C， 第三区 115-120°C， 第四区 120-125 °C , 第五区 120-125°C , 第六区 120-130°C， 第七区 125-130°C  In the step (2), the single-screw extruder is divided into seven zones, and the operating temperatures of the zones are: 110-115 °C in the first zone, 115-120 °C in the second zone, and 115-120° in the third zone. C, the fourth zone is 120-125 °C, the fifth zone is 120-125 °C, the sixth zone is 120-130 °C, and the seventh zone is 125-130 °C.
所述步骤 (3 )中，挤出机分为四个区，各区的工作温度为：第一区 150-160 °C， 第二区 165-175°C， 第三区 165-175°C， 第四区 170-180°C。 In the step (3), the extruder is divided into four zones, and the working temperature of each zone is: the first zone is 150-160 ° C, The second zone is 165-175 ° C, the third zone is 165-175 ° C, and the fourth zone is 170-180 ° C.
实施例 3  Example 3
一种 125°C辐照交联 EPCV光伏用低烟无卤护套电缆材料， 按重量份数主 要由以下原料制成： 三元乙丙橡胶 （EPDM): 18份； 热塑性弹性体 （TPE): 2 份； 聚乙烯： 5份； 乙烯 -醋酸乙烯共聚物： 12份； 相容剂： 2; 氢氧化铝 59份; 安定剂： 2份； 硅酮母粒： 2份。  A low-smoke halogen-free sheathed cable material for 125 ° C irradiation cross-linked EPCV photovoltaic, mainly made of the following raw materials by weight: EPDM: 18 parts; thermoplastic elastomer (TPE) : 2 parts; Polyethylene: 5 parts; Ethylene-vinyl acetate copolymer: 12 parts; Compatibilizer: 2; Aluminium hydroxide 59 parts; Stabilizer: 2 parts; Silicone masterbatch: 2 parts.
所述的三元乙丙橡胶 （EPDM) 乙烯丙烯链段摩尔比为 60:40， 第三单体为 乙叉冰片烯， 第三单体占三种单体的总质量的质量百分比为 3%， 数均分子量为 15万， 100 °C门尼粘度为 50 Pa's, 邵氏 A硬度为 40。  The ethylene propylene rubber (EPDM) ethylene propylene segment molar ratio is 60:40, the third monomer is ethylidene borneene, and the third monomer accounts for 3% by mass of the total mass of the three monomers. The number average molecular weight is 150,000, the Mooney viscosity at 100 °C is 50 Pa's, and the Shore A hardness is 40.
所述的热塑性弹性体（TPE)为乙烯-丙烯共聚物，数均分子量 15万， 100°C 门尼粘度为 50 Pa's，邵氏 A硬度为 60， 190 °C和 2.16kg下熔融指数为 1-5 g/10min。  The thermoplastic elastomer (TPE) is an ethylene-propylene copolymer having a number average molecular weight of 150,000, a Mooney viscosity of 50 Pa's at 100 ° C, a Shore A hardness of 60, a melt index of 1 at 190 ° C and 2.16 kg. -5 g/10min.
所述的聚乙烯为低密度聚乙烯， 数均分子量 8万， 190°C和 2.16kg下熔融 指数为 5 g/10min。  The polyethylene is a low density polyethylene having a number average molecular weight of 80,000 and a melt index of 5 g/10 min at 190 ° C and 2.16 kg.
所述的乙烯-醋酸乙烯共聚物的醋酸乙烯含量为 50wt%， 190°C和 2.16kg下 熔融指数为 5 g/10min。  The ethylene-vinyl acetate copolymer had a vinyl acetate content of 50% by weight, and a melt index of 5 g/10 min at 190 ° C and 2.16 kg.
所述的相容剂为马来酸酐接枝聚乙烯， 接枝率为 2%， 190°C和 2.16kg下熔 融指数为 2 g/10min  The compatibilizer is maleic anhydride grafted polyethylene with a graft ratio of 2%, a melting index of 2 g/10 min at 190 ° C and 2.16 kg.
所述的氢氧化铝为拜耳-烧结联合法制备的， 采用氨基硅垸进行改性， 其粒 径 D50为 2微米， 目数 5000目。  The aluminum hydroxide is prepared by a Bayer-sintering combination method and modified by aminosilicone, and has a particle diameter D50 of 2 μm and a mesh number of 5,000 mesh.
所述的安定剂由 -下述组分按重量份组成： 硬脂酸钙： 40份， 硬脂酸锌： 10 份， 四 [β-(3,5-二叔丁基 -4-羟基苯基)丙酸酯]季戊四醇酯： 50份。  The stabilizer is composed of - the following components in parts by weight: calcium stearate: 40 parts, zinc stearate: 10 parts, tetra [β-(3,5-di-tert-butyl-4-hydroxybenzene) Propionate] pentaerythritol ester: 50 parts.
所述的硅酮母粒由下述组分按重量份组成： 低密度聚乙烯： 10份， 硅氧垸： 50份， 二氧化硅： 40份。所述的低密度聚乙烯数均分子量 5万， 190°C和 2.16kg 下的熔融指数 9 g/10min。 所述的硅氧垸为甲基乙烯基硅氧垸， 数均分子量 80 万。 所述的二氧化硅为沉淀法二氧化硅， 目数 6000目。 The silicone masterbatch is composed of the following components in parts by weight: low density polyethylene: 10 parts, siloxane: 50 parts, silica: 40 parts. The low density polyethylene has a number average molecular weight of 50,000, 190 ° C and 2.16 kg. The melt index below is 9 g/10 min. The siloxane is methyl vinyl siloxane with a number average molecular weight of 800,000. The silica is precipitated silica having a mesh number of 6,000 mesh.
上述 125°C辐照交联 EPCV光伏用低烟无卤护套电缆材料制备方法包括如 下步骤：  The above 125 ° C irradiation cross-linked EPCV photovoltaic low-smoke halogen-free sheathed cable material preparation method comprises the following steps:
( 1 ) 准确称量配方各组分；  (1) accurately weigh the components of the formula;
(2 ) 将称量好的原料通过密炼机熔融共混然后依次通过单螺杆挤出机造 粒；  (2) The weighed raw materials are melt blended through an internal mixer and then sequentially granulated by a single screw extruder;
(3 ) 将造好的粒子通过挤出机挤出线材。  (3) The extruded particles are extruded through an extruder.
(4 ) 线材经过电子加速器进行辐照交联。  (4) The wire is irradiated and crosslinked by an electron accelerator.
将各组分通过密炼机熔融共混， 具体参数为： 密炼温度为 160-175°C， 密炼 时间为 15-25分钟。  The components are melt blended by an internal mixer. The specific parameters are: the mixing temperature is 160-175 ° C, and the mixing time is 15-25 minutes.
所述步骤（2 ) 中， 单螺杆挤出机分为七个区， 各区的工作温度为： 第一区 110-115 °C , 第二区 115-120°C， 第三区 115-120°C， 第四区 120-125 °C , 第五区 120-125°C , 第六区 120-130°C， 第七区 125-130°C  In the step (2), the single-screw extruder is divided into seven zones, and the operating temperatures of the zones are: 110-115 °C in the first zone, 115-120 °C in the second zone, and 115-120° in the third zone. C, the fourth zone is 120-125 °C, the fifth zone is 120-125 °C, the sixth zone is 120-130 °C, and the seventh zone is 125-130 °C.
所述步骤 (3 )中，挤出机分为四个区，各区的工作温度为：第一区 150-160 °C， 第二区 165-175 °C， 第三区 165-175 °C， 第四区 170-180°C。  In the step (3), the extruder is divided into four zones, and the working temperature of each zone is: first zone 150-160 °C, second zone 165-175 °C, third zone 165-175 °C, The fourth zone is 170-180 °C.
实施例 4  Example 4
一种 125°C辐照交联 EPCV光伏用低烟无卤护套电缆材料， 按重量份数主 要由以下原料制成： 三元乙丙橡胶 （EPDM): 16 份； 热塑性弹性体 （TPE): 1.5份； 聚乙烯： 8份； 乙烯 -醋酸乙烯共聚物： 12份； 相容剂： 2.5 ; 氢氧化铝 56份； 安定剂： 2份； 硅酮母粒： 2份。  A low-smoke halogen-free sheathed cable material for 125 ° C irradiation cross-linked EPCV photovoltaic, mainly made of the following raw materials by weight: EPDM: 16 parts; thermoplastic elastomer (TPE) : 1.5 parts; Polyethylene: 8 parts; Ethylene-vinyl acetate copolymer: 12 parts; Compatibilizer: 2.5; Aluminium hydroxide 56 parts; Stabilizer: 2 parts; Silicone masterbatch: 2 parts.
所述的三元乙丙橡胶 （EPDM) 乙烯丙烯链段摩尔比为 60:40， 第三单体为 乙叉冰片烯， 第三单体占三种单体的总质量的质量百分比为 3%， 数均分子量为 15万， 100 °C门尼粘度为 50 Pa's, 邵氏 A硬度为 40。 The ethylene propylene rubber (EPDM) ethylene propylene segment molar ratio is 60:40, the third monomer is ethylidene borneene, and the third monomer accounts for 3% by mass of the total mass of the three monomers. , the number average molecular weight is 150,000, the Mooney viscosity at 100 °C is 50 Pa's, and the Shore A hardness is 40.
所述的热塑性弹性体（TPE)为乙烯-丙烯共聚物，数均分子量 15万， 100°C 门尼粘度为 50 Pa's，邵氏 A硬度为 60， 190 °C和 2.16kg下熔融指数为 1-5 g/10min。  The thermoplastic elastomer (TPE) is an ethylene-propylene copolymer having a number average molecular weight of 150,000, a Mooney viscosity of 50 Pa's at 100 ° C, a Shore A hardness of 60, a melt index of 1 at 190 ° C and 2.16 kg. -5 g/10min.
所述的聚乙烯为低密度聚乙烯， 数均分子量 8万， 190°C和 2.16kg下熔融 指数为 5 g/10min。  The polyethylene is a low density polyethylene having a number average molecular weight of 80,000 and a melt index of 5 g/10 min at 190 ° C and 2.16 kg.
所述的乙烯-醋酸乙烯共聚物的醋酸乙烯含量为 50wt%， 190°C和 2.16kg下 熔融指数为 5 g/10min。  The ethylene-vinyl acetate copolymer had a vinyl acetate content of 50% by weight, and a melt index of 5 g/10 min at 190 ° C and 2.16 kg.
所述的相容剂为马来酸酐接枝聚乙烯， 接枝率为 2%， 190°C和 2.16kg下熔 融指数为 2 g/10min。  The compatibilizer is maleic anhydride grafted polyethylene having a graft ratio of 2%, a melt index of 2 g/10 min at 190 ° C and 2.16 kg.
所述的氢氧化铝为拜耳-烧结联合法制备的， 采用氨基硅垸进行改性， 其粒 径 D50为 2微米， 目数 5000目。  The aluminum hydroxide is prepared by a Bayer-sintering combination method and modified by aminosilicone, and has a particle diameter D50 of 2 μm and a mesh number of 5,000 mesh.
所述的安定剂由下述组分按重量份组成： 硬脂酸钙： 40份， 硬脂酸锌： 10 份， 四 [β-(3,5-二叔丁基 -4-羟基苯基)丙酸酯]季戊四醇酯： 50份。  The stabilizer is composed of the following components in parts by weight: calcium stearate: 40 parts, zinc stearate: 10 parts, tetra [β-(3,5-di-tert-butyl-4-hydroxyphenyl) Propionate] pentaerythritol ester: 50 parts.
所述的硅酮母粒由下述组分按重量份组成： 低密度聚乙烯： 10份， 硅氧垸： 50份， 二氧化硅： 40份。所述的低密度聚乙烯数均分子量 5万， 190°C和 2.16kg 下的熔融指数 9 g/10min。 所述的硅氧垸为甲基乙烯基硅氧垸， 数均分子量 80 万。 所述的二氧化硅为沉淀法二氧化硅， 目数 6000目。  The silicone masterbatch is composed of the following components in parts by weight: low density polyethylene: 10 parts, siloxane: 50 parts, silica: 40 parts. The low density polyethylene has a number average molecular weight of 50,000, a melt index of 9 g/10 min at 190 ° C and 2.16 kg. The siloxane is methyl vinyl siloxane with a number average molecular weight of 800,000. The silica was precipitated silica having a mesh size of 6,000 mesh.
上述 125°C辐照交联 EPCV光伏用低烟无卤护套电缆材料制备方法包括步 骤：  The above method for preparing 125 ° C radiation cross-linked EPCV photovoltaic low-smoke halogen-free sheathed cable material comprises the steps of:
( 1 ) 准确称量配方各组分；  (1) accurately weigh the components of the formula;
(2 ) 将称量好的原料通过密炼机熔融共混然后依次通过单螺杆挤出机造 粒；  (2) The weighed raw materials are melt blended through an internal mixer and then sequentially granulated by a single screw extruder;
(3 ) 将造好的粒子通过挤出机挤出线材。 (4 ) 线材经过电子加速器进行辐照交联。 (3) The extruded particles are extruded through an extruder. (4) The wire is irradiated and crosslinked by an electron accelerator.
将各组分通过密炼机熔融共混， 具体参数为： 密炼温度为 160-175°C， 密炼 时间为 15-25分钟。  The components are melt blended by an internal mixer. The specific parameters are: the mixing temperature is 160-175 ° C, and the mixing time is 15-25 minutes.
所述步骤（2 ) 中， 单螺杆挤出机分为七个区， 各区的工作温度为： 第一区 110-115 °C , 第二区 115-120°C， 第三区 115-120°C， 第四区 120-125 °C , 第五区 120-125°C , 第六区 120-130°C， 第七区 125-130°C  In the step (2), the single-screw extruder is divided into seven zones, and the operating temperatures of the zones are: 110-115 °C in the first zone, 115-120 °C in the second zone, and 115-120° in the third zone. C, the fourth zone is 120-125 °C, the fifth zone is 120-125 °C, the sixth zone is 120-130 °C, and the seventh zone is 125-130 °C.
所述步骤 (3 )中，挤出机分为四个区，各区的工作温度为：第一区 150-160 °C， 第二区 165-175 °C， 第三区 165-175 °C， 第四区 170-180°C。  In the step (3), the extruder is divided into four zones, and the working temperature of each zone is: first zone 150-160 °C, second zone 165-175 °C, third zone 165-175 °C, The fourth zone is 170-180 °C.
实施例 5  Example 5
一种 125°C辐照交联 EPCV光伏用低烟无卤护套电缆材料， 按重量份数主 要由以下原料制成： 三元乙丙橡胶 （EPDM): 10份； 聚乙烯： 25份； 相容剂： 1份； 氢氧化铝 45份； 安定剂： 1份； 硅酮母粒： 1份。  A 125 ° C irradiation cross-linked EPCV photovoltaic low-smoke halogen-free sheathed cable material, which is mainly made up of the following raw materials by weight: EPDM: 10 parts; Polyethylene: 25 parts; Compatibilizer: 1 part; 45 parts of aluminum hydroxide; stabilizer: 1 part; silicone masterbatch: 1 part.
所述的三元乙丙橡胶 （EPDM) 乙烯丙烯链段摩尔比为 60:40， 第三单体为 乙叉冰片烯， 第三单体占三种单体的总质量的质量百分比为 1%， 数均分子量为 5万， 100 °C门尼粘度为 30 Pa's, 邵氏 A硬度为 20。。  The ethylene propylene rubber (EPDM) ethylene propylene segment molar ratio is 60:40, the third monomer is ethylidene borneene, and the third monomer accounts for 1% by mass of the total mass of the three monomers. The number average molecular weight is 50,000, the Mooney viscosity at 100 °C is 30 Pa's, and the Shore A hardness is 20. .
所述的聚乙烯为低密度聚乙烯， 数均分子量 5万， 190°C和 2.16kg下熔融 指数为 3.6 g/10min。  The polyethylene is a low density polyethylene having a number average molecular weight of 50,000, a melt index of 3.6 g/10 min at 190 ° C and 2.16 kg.
所述的相容剂为马来酸酐接枝聚乙烯， 接枝率为 1%， 190°C和 2.16kg下熔 融指数为 1 g/10min。  The compatibilizing agent is maleic anhydride grafted polyethylene, and the graft ratio is 1%, and the melting index is 1 g/10 min at 190 ° C and 2.16 kg.
所述的氢氧化铝为拜耳-烧结联合法制备的， 采用氨基硅垸进行改性， 其粒 径 D50为 1微米， 目数 4000目。  The aluminum hydroxide is prepared by a Bayer-sintering combination method, and is modified by aminosilicone, and has a particle diameter D50 of 1 μm and a mesh number of 4000 mesh.
所述的安定剂由下述组分按重量份组成： 硬脂酸钙： 35 份， 硬脂酸锌： 5 份， 四 [β-(3,5-二叔丁基 -4-羟基苯基)丙酸酯]季戊四醇酯： 60份。 所述的硅酮母粒由下述组分按重量份组成： 低密度聚乙烯： 10份， 硅氧垸： 45份， 二氧化硅： 15份。所述的低密度聚乙烯数均分子量 5万， 190°C和 2.16kg 下的熔融指数 5 g/10min。 所述的硅氧垸为甲基乙烯基硅氧垸， 数均分子量 60 万。 所述的二氧化硅为沉淀法二氧化硅， 目数 5000目。 The stabilizer is composed of the following components in parts by weight: calcium stearate: 35 parts, zinc stearate: 5 parts, tetra [β-(3,5-di-tert-butyl-4-hydroxyphenyl) Propionate] pentaerythritol ester: 60 parts. The silicone masterbatch consists of the following components in parts by weight: low density polyethylene: 10 parts, siloxane: 45 parts, silica: 15 parts. The low density polyethylene has a number average molecular weight of 50,000, a melt index of 5 g/10 min at 190 ° C and 2.16 kg. The siloxane is methyl vinyl siloxane with a number average molecular weight of 600,000. The silica is precipitated silica having a mesh number of 5,000 mesh.
采用与实施例 1相同的方法制备上述 125°C辐照交联 EPCV光伏用低烟无 卤护套电缆材料。  The above-mentioned 125 ° C irradiation crosslinked EPCV photovoltaic low-smoke halogen-free sheathed cable material was prepared in the same manner as in Example 1.
实施例 6  Example 6
一种 125°C辐照交联 EPCV光伏用低烟无卤护套电缆材料， 按重量份数主 要由以下原料制成： 三元乙丙橡胶 （EPDM): 20份； 热塑性弹性体 （TPE): 5 份； 乙烯 -醋酸乙烯共聚物： 5份； 相容剂： 5; 氢氧化铝 65份； 安定剂： 3份; 硅酮母粒： 3份。  A low-smoke halogen-free sheathed cable material for 125 ° C irradiation cross-linked EPCV photovoltaic, mainly made of the following raw materials by weight: EPDM: 20 parts; thermoplastic elastomer (TPE) : 5 parts; ethylene-vinyl acetate copolymer: 5 parts; compatibilizer: 5; 65 parts of aluminum hydroxide; stabilizer: 3 parts; silicone masterbatch: 3 parts.
所述的三元乙丙橡胶 （EPDM) 乙烯丙烯链段摩尔比为 70:30， 第三单体为 乙叉冰片烯， 第三单体占三种单体的总质量的质量百分比为 2%， 数均分子量为 10万， 100°C门尼粘度为 70 Pa-s， 邵氏 A硬度为 50。  The ethylene propylene rubber (EPDM) ethylene propylene segment molar ratio is 70:30, the third monomer is ethylidene norbornene, and the third monomer accounts for 2% by mass of the total mass of the three monomers. The number average molecular weight is 100,000, the Mooney viscosity at 100 ° C is 70 Pa-s, and the Shore A hardness is 50.
所述的热塑性弹性体（TPE)为乙烯-丙烯共聚物，数均分子量 10万， 100°C 门尼粘度为 30 Pa s,邵氏 A硬度为 30， 190°C和 2.16kg下熔融指数为 4 g/10min。  The thermoplastic elastomer (TPE) is an ethylene-propylene copolymer having a number average molecular weight of 100,000, a Mooney viscosity of 100 Pa at 100 ° C, a Shore A hardness of 30, a melt index of 190 ° C and 2.16 kg. 4 g/10min.
所述的乙烯-醋酸乙烯共聚物的醋酸乙烯含量为 60wt%， 190°C和 2.16kg下 熔融指数为 5 g/10min。  The ethylene-vinyl acetate copolymer had a vinyl acetate content of 60% by weight, and a melt index of 5 g/10 min at 190 ° C and 2.16 kg.
所述的相容剂为马来酸酐接枝聚乙烯， 接枝率为 1.5%， 190°C和 2.16kg下 熔融指数为 3 g/10min。  The compatibilizing agent is a maleic anhydride grafted polyethylene having a graft ratio of 1.5%, a melt index of 3 g/10 min at 190 ° C and 2.16 kg.
所述的氢氧化铝为拜耳-烧结联合法制备的， 采用氨基硅垸进行改性， 其粒 径 D50为 2微米， 目数 8000目。  The aluminum hydroxide is prepared by a Bayer-sintering combination method and modified by aminosilicone, and has a particle diameter D50 of 2 μm and a mesh size of 8000 mesh.
所述的安定剂由下述组分按重量份组成： 硬脂酸钙： 55份， 硬脂酸锌： 35 份， 四 [β-(3,5-二叔丁基 -4-羟基苯基)丙酸酯]季戊四醇酯： 35份。 The stabilizer is composed of the following components in parts by weight: calcium stearate: 55 parts, zinc stearate: 35 Parts, tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] pentaerythritol ester: 35 parts.
所述的硅酮母粒由下述组分按重量份组成： 低密度聚乙烯： 20份， 硅氧垸： The silicone masterbatch is composed of the following components in parts by weight: Low density polyethylene: 20 parts, siloxane:
75份，二氧化硅： 55份。所述的低密度聚乙烯数均分子量 10万， 190 °C和 2.16kg 下的熔融指数 10 g/10min。所述的硅氧垸为甲基乙烯基硅氧垸， 数均分子量 100 万。 所述的二氧化硅为沉淀法二氧化硅， 目数 5000目。 75 parts, silica: 55 parts. The low density polyethylene has a number average molecular weight of 100,000, a melt index of 10 g/10 min at 190 ° C and 2.16 kg. The siloxane is methyl vinyl siloxane with a number average molecular weight of 1 million. The silica is precipitated silica having a mesh number of 5,000 mesh.
采用与实施例 1相同的方法制备上述 125°C辐照交联 EPCV光伏用低烟无 卤护套电缆材料。  The above-mentioned 125 ° C irradiation crosslinked EPCV photovoltaic low-smoke halogen-free sheathed cable material was prepared in the same manner as in Example 1.
实施例 7  Example 7
一种 125°C辐照交联 EPCV光伏用低烟无卤护套电缆材料， 按重量份数主 要由以下原料制成： 三元乙丙橡胶 （EPDM): 14份； 热塑性弹性体 （TPE): 4 份； 聚乙烯： 10份； 乙烯 -醋酸乙烯共聚物： 8份； 相容剂： 2; 氢氧化铝 60份; 安定剂： 2份； 硅酮母粒： 2份。  A low-smoke halogen-free sheathed cable material for 125 ° C irradiation cross-linked EPCV photovoltaic, mainly made of the following raw materials by weight: EPDM: 14 parts; thermoplastic elastomer (TPE) : 4 parts; Polyethylene: 10 parts; Ethylene-vinyl acetate copolymer: 8 parts; Compatibilizer: 2; 60 parts of aluminum hydroxide; Stabilizer: 2 parts; Silicone masterbatch: 2 parts.
所述的三元乙丙橡胶 （EPDM) 乙烯丙烯链段摩尔比为 60:40， 第三单体为 乙叉冰片烯， 第三单体占三种单体的总质量的质量百分比为 2%， 数均分子量为 10万， 100 °C门尼粘度为 50 Pa's, 邵氏 A硬度为 40。  The ethylene propylene rubber (EPDM) ethylene propylene segment molar ratio is 60:40, the third monomer is ethylidene borneene, and the third monomer accounts for 2% by mass of the total mass of the three monomers. The number average molecular weight is 100,000, the Mooney viscosity at 100 °C is 50 Pa's, and the Shore A hardness is 40.
所述的热塑性弹性体 （TPE) 为乙烯〜丙烯共聚物， 其数均分子量 15万， 100°C门尼粘度为 60Pa-s, 邵氏 A硬度为 50， 190°C和 2.16kg下的熔融指数为 1-5 g/10min。  The thermoplastic elastomer (TPE) is an ethylene-propylene copolymer having a number average molecular weight of 150,000, a Mooney viscosity of 100 Pa-s at 100 ° C, a Shore A hardness of 50, melting at 190 ° C and 2.16 kg. The index is 1-5 g/10 min.
所述聚乙烯为低密度聚乙烯， 数均分子量 8万， 190°C和 2.16kg下熔融指 数为 3g/10min。  The polyethylene was a low density polyethylene having a number average molecular weight of 80,000, and a melting index of 3 g/10 min at 190 ° C and 2.16 kg.
所述乙烯-醋酸乙烯共聚物的醋酸乙烯含量为 50%， 190°C和 2.16kg下熔融 指数为 4 g/10min。  The ethylene-vinyl acetate copolymer had a vinyl acetate content of 50%, and a melt index of 4 g/10 min at 190 ° C and 2.16 kg.
所述的相容剂为马来酸酐接枝聚乙烯， 接枝率为 1.5%， 190°C和 2.16kg下 熔融指数为 2 g/10min。 所述的氢氧化铝为拜耳-烧结联合法制备的， 采用氨基硅垸进行改性， 其粒 径 D50为 1微米， 目数 5000目。 The compatibilizer is maleic anhydride grafted polyethylene, and the graft ratio is 1.5%, 190 ° C and 2.16 kg. The melt index is 2 g/10 min. The aluminum hydroxide is prepared by a Bayer-sintering combination method and is modified by aminosilicone, and has a particle diameter D50 of 1 micrometer and a mesh number of 5,000 mesh.
所述安定剂由下述组分按重量份组成：硬脂酸钙： 40份，硬脂酸锌： 10份， 四 [β-(3,5-二叔丁基 -4-羟基苯基)丙酸酯]季戊四醇酯： 50份。  The stabilizer is composed of the following components in parts by weight: calcium stearate: 40 parts, zinc stearate: 10 parts, tetra [β-(3,5-di-tert-butyl-4-hydroxyphenyl) Propionate] pentaerythritol ester: 50 parts.
所述硅酮母粒由下述组分按重量份组成： 低密度聚乙烯： 10份， 硅氧垸： 50份， 二氧化硅： 40份。 所述低密度聚乙烯数均分子量 8万， 190°C和 2.16kg 下的熔融指数 8 g/10min。 所述的硅氧垸为甲基乙烯基硅氧垸， 数均分子量 80 万。 所述的二氧化硅为沉淀法二氧化硅， 目数 5500目。  The silicone masterbatch is composed by weight of the following components: Low density polyethylene: 10 parts, siloxane: 50 parts, silica: 40 parts. The low density polyethylene has a number average molecular weight of 80,000, a melt index of 8 g/10 min at 190 ° C and 2.16 kg. The siloxane is methyl vinyl siloxane with a number average molecular weight of 800,000. The silica was precipitated silica having a mesh number of 5,500 mesh.
采用与实施例 1相同的方法制备 125°C辐照交联 EPCV光伏用低烟无卤护 套电缆材料。  A low-smoke halogen-free sheath cable material for 125 ° C irradiation cross-linked EPCV photovoltaic was prepared in the same manner as in Example 1.
对实施例 1-7的 125°C辐照交联 EPCV光伏用低烟无卤护套电缆材料进行性 能测试， 具体数据见下表： 实施例 实施例 实施例 实施例  The performance test of the 125 ° C irradiation cross-linked EPCV photovoltaic low-smoke halogen-free sheathed cable material of Examples 1-7 was carried out. The specific data are shown in the following table: EXAMPLES EXAMPLES EXAMPLES
测试项目 实施例 5 实施例 6 实施例 7  Test item Example 5 Example 6 Example 7
1 2 3 4 抗张强度 11.2MPa 10.9MPa ll.OMPa 11.5MPa 12.2MPa 11.6MPa 11.4MPa 断裂伸长  1 2 3 4 Tensile strength 11.2MPa 10.9MPa ll.OMPa 11.5MPa 12.2MPa 11.6MPa 11.4MPa Elongation at break
192% 201% 186% 196% 186% 185% 189% 烟中透光  192% 201% 186% 196% 186% 185% 189% smoke in the light
95% 92% 95% 93% 96% 95% 93%  95% 92% 95% 93% 96% 95% 93%
VW-1垂 VW-1 vertical
直燃烧测 pass pass pass pass pass pass pass 试  Straight burning test pass pass pass pass pass pass pass
耐油 抗  Oil resistant
52% 50% 49% 56% 51% 49% 50% 试验 张 121 °C 强 52% 50% 49% 56% 51% 49% 50% Test Zhang Strong at 121 °C
* 18H 度  * 18H degrees
保  Guarantee
持  Hold
断 Broken
裂  Crack
伸  Stretch
长 82% 79% 85% 81% 82% 85% 79% 保  Length 82% 79% 85% 81% 82% 85% 79% Guarantee
持  Hold
率  Rate
申请人声明， 本发明通过上述实施例来说明本发明的详细组成及方法， 但 本发明并不局限于上述详细组成及方法， 即不意味着本发明必须依赖上述详细 组成及方法才能实施。 所属技术领域的技术人员应该明了， 对本发明的任何改 进， 对本发明产品各原料的等效替换及辅助组分的添加、 具体方式的选择等， 均落在本发明的保护范围和公开范围之内。 The Applicant claims that the present invention is not limited to the above-described detailed compositions and methods, and the present invention is not limited to the above-described detailed compositions and methods. It should be apparent to those skilled in the art that any modification of the present invention, equivalent replacement of each raw material of the product of the present invention, addition of auxiliary components, selection of specific means, etc., fall within the scope of protection and disclosure of the present invention. .

Claims

权 利 要 求 书 claims
1、 一种 125 °C辐照交联 EPCV光伏用无卤阻燃护套材料， 其特征在于， 其 按重量份数主要由以下原料制成： 1. A 125 °C radiation cross-linked halogen-free flame retardant sheath material for EPCV photovoltaics, characterized in that it is mainly made of the following raw materials in parts by weight:
三元乙丙橡胶 10〜20份 EPDM rubber 10~20 parts
热塑性弹性体 乙烯-醋酸乙烯共聚物 Thermoplastic elastomer ethylene-vinyl acetate copolymer
相
Figure imgf000020_0001
容剂 Mutually
Figure imgf000020_0001
Container
45-65份 45-65 servings
安定剂 stabilizer
Figure imgf000020_0002
Figure imgf000020_0002
2、 如权利要求 1所述的无卤阻燃护套材料， 其特征在于， 其按重量份数主 要由以下原料制成： 2. The halogen-free flame retardant sheath material as claimed in claim 1, characterized in that it is mainly made of the following raw materials in parts by weight:
三元乙丙橡胶 10.5〜18.5份 EPDM rubber 10.5~18.5 parts
热塑性弹性体 0.5〜5份 Thermoplastic elastomer 0.5~5 parts
聚乙烯 0.5-25份 Polyethylene 0.5-25 parts
乙烯-醋酸乙烯共聚物 0.5-15份 Ethylene-vinyl acetate copolymer 0.5-15 parts
相容剂 1〜5份 Compatibilizer 1~5 parts
48-62份 48-62 servings
安定剂 1〜3份 Stabilizer 1 to 3 parts
1〜3份。 1 to 3 servings.
3、 如权利要求 1或 2所述的无卤阻燃护套材料， 其特征在于， 其按重量份 数主要由以下原料制成: 3. The halogen-free flame retardant sheath material as claimed in claim 1 or 2, characterized in that it is mainly made of the following raw materials in parts by weight:
三元乙丙橡胶 11〜18份 热塑性弹性体 1〜5份 EPDM rubber 11 to 18 parts 1 to 5 parts of thermoplastic elastomer
聚乙烯 2-23份 Polyethylene 2-23 parts
乙烯-醋酸乙烯共聚物 2〜15份 Ethylene-vinyl acetate copolymer 2 to 15 parts
相容剂 1〜5份 Compatibilizer 1~5 parts
氢氧化铝 50-60份 Aluminum hydroxide 50-60 parts
安定剂 1〜3份 Stabilizer 1 to 3 parts
硅酮母粒 1〜3份。 Silicone masterbatch 1~3 parts.
4、 如权利要求 1-3之一所述的无卤阻燃护套材料， 其特征在于， 所述三元 乙丙橡胶乙烯丙烯链段摩尔比为 60:40〜70:30， 第三单体为乙叉冰片烯， 第三单 体占三种单体的总质量的质量百分比为 1〜3%，数均分子量为 5〜15万， 100°C门 尼粘度为 30〜70 P^s， 邵氏 A硬度为 20〜50； 4. The halogen-free flame retardant sheath material according to one of claims 1 to 3, characterized in that the molar ratio of the ethylene propylene segment of the EPDM rubber is 60:40~70:30, and the third unit The monomer is ethylidenebornene, the third monomer accounts for 1 to 3% of the total mass of the three monomers, the number average molecular weight is 50,000 to 150,000, and the Mooney viscosity at 100°C is 30 to 70 P^s , Shore A hardness is 20~50;
优选地，所述热塑性弹性体为乙烯-丙烯共聚物，其数均分子量为 10〜20万， 100°C门尼粘度为 30〜60 Pa-s， 邵氏 A硬度为 30〜60， 190°C和 2.16kg下的熔融 指数为 1〜5 g/10min。 Preferably, the thermoplastic elastomer is an ethylene-propylene copolymer with a number average molecular weight of 100,000 to 200,000, a Mooney viscosity of 30 to 60 Pa-s at 100°C, and a Shore A hardness of 30 to 60, 190° The melt index at C and 2.16kg is 1~5 g/10min.
5、 如权利要求 1-4之一所述的无卤阻燃护套材料， 其特征在于， 所述聚乙 烯为低密度聚乙烯， 数均分子量 5〜15万， 190°C和 2.16kg下的熔融指数为 1〜5 g/10min; 5. The halogen-free flame retardant sheath material according to one of claims 1 to 4, characterized in that the polyethylene is low density polyethylene, with a number average molecular weight of 50,000 to 150,000, at 190°C and 2.16kg. The melt index is 1~5 g/10min;
优选地， 所述乙烯-醋酸乙烯共聚物的醋酸乙烯含量为 40〜60wt%， 190°C和 2.16kg下的熔融指数为 3〜5 g/10min。 Preferably, the vinyl acetate content of the ethylene-vinyl acetate copolymer is 40~60wt%, and the melt index at 190°C and 2.16kg is 3~5 g/10min.
6、 如权利要求 1-5之一所述的无卤阻燃护套材料， 其特征在于， 所述相容 剂为马来酸酐接枝聚乙烯，接枝率为 1〜2%，190°C和 2.16kg下的熔融指数为 1〜3 g/10min; 6. The halogen-free flame retardant sheath material according to one of claims 1 to 5, characterized in that the compatibilizer is maleic anhydride grafted polyethylene, the grafting rate is 1~2%, 190° The melt index at C and 2.16kg is 1~3 g/10min;
优选地， 所述氢氧化铝为拜耳 -烧结联合法制备； 优选地， 所述氢氧化铝采 用氨基硅垸进行改性， 其粒径 D50为 1〜2微米， 目数 4000〜8000目。 Preferably, the aluminum hydroxide is prepared by Bayer-sintering combined method; Preferably, the aluminum hydroxide is prepared by Modified with aminosilane, the particle size D50 is 1 to 2 microns, and the mesh number is 4000 to 8000 mesh.
7、 如权利要求 1-6之一所述的无卤阻燃护套材料， 其特征在于， 所述安定 剂由下述组分按重量份组成： 硬脂酸钙 35〜55份， 硬脂酸锌 5〜35份， 四 [β-(3,5- 二叔丁基 -4-羟基苯基)丙酸酯]季戊四醇酯 35〜60份。 7. The halogen-free flame retardant sheath material according to one of claims 1 to 6, characterized in that the stabilizer is composed of the following components by weight: 35 to 55 parts of calcium stearate, stearin 5 to 35 parts of zinc acid, 35 to 60 parts of tetrakis [β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol ester.
8、 如权利要求 1-7之一所述的无卤阻燃护套材料， 其特征在于， 所述硅酮 母粒由下述组分按重量份组成： 10〜20份低密度聚乙烯， 45〜75份硅氧垸， 15-55 份二氧化硅； 8. The halogen-free flame retardant sheath material according to one of claims 1 to 7, characterized in that the silicone masterbatch is composed of the following components by weight: 10 to 20 parts of low density polyethylene, 45~75 parts of silicone, 15-55 parts of silica;
优选地， 所述的低密度聚乙烯数均分子量 5〜10万， 190°C和 2.16kg下的熔 融指数 5〜10 g/10min; Preferably, the low-density polyethylene has a number average molecular weight of 5 to 100,000 and a melt index of 5 to 10 g/10 min at 190°C and 2.16kg ;
优选地， 所述硅氧垸为甲基乙烯基硅氧垸， 数均分子量 60〜100万； 优选地， 所述二氧化硅为沉淀法二氧化硅， 目数 5000〜6000目。 Preferably, the silica is methyl vinyl siloxane, with a number average molecular weight of 600,000 to 1,000,000; Preferably, the silica is precipitated silica, with a mesh number of 5000~6000.
9、 一种如权利要求 1-8之一所述的 125°C辐照交联 EPCV光伏用无卤阻燃 护套材料的制备方法， 其特征在于， 所述方法包括如下步骤： 9. A method for preparing a 125°C radiation cross-linked halogen-free flame retardant sheath material for EPCV photovoltaics as described in one of claims 1 to 8, characterized in that the method includes the following steps:
( 1 )将配方量的各组分通过密炼机熔融共混，然后通过单螺杆挤出机造粒; (1) Melt and blend the ingredients in the formula through an internal mixer, and then pelletize through a single-screw extruder;
(2 ) 将步骤 （1 ) 得到的粒子通过挤出机挤出线材； (2) Extrude the particles obtained in step (1) into wires through an extruder;
(3 )线材经过电子加速器进行辐照交联， 得到 125°C辐照交联 EPCV光伏 用无卤阻燃护套材料。 (3) The wire is irradiated and cross-linked through an electron accelerator to obtain a 125°C irradiation cross-linked halogen-free flame retardant sheath material for EPCV photovoltaics.
10、 如权利要求 9 所述的方法， 其特征在于， 步骤 （1 ) 的密炼温度为 160〜175°C， 密炼时间为 15〜25分钟； 10. The method according to claim 9, characterized in that the internal mixing temperature of step (1) is 160~175°C, and the internal mixing time is 15~25 minutes;
优选地， 步骤（1 )所述单螺杆挤出机分为七个区， 各区的工作温度为： 第 一区 110〜115°C， 第二区 115〜120°C， 第三区 115〜120°C， 第四区 120〜125 °C， 第五区 120〜125 °C， 第六区 120〜130°C， 第七区 125〜130°C ; Preferably, the single-screw extruder in step (1) is divided into seven zones, and the working temperature of each zone is: 110~115°C in the first zone, 115~120°C in the second zone, 115~120°C in the third zone °C, the fourth zone is 120~125°C, the fifth zone is 120~125°C, the sixth zone is 120~130°C, the seventh zone is 125~130°C;
优选地， 步骤（2) 中所述挤出机分为四个区， 各区的工作温度为： 第一区 150-160 °C, 第二区 165〜175°C， 第三区 165〜175°C， 第四区 170〜180°C。 Preferably, the extruder described in step (2) is divided into four zones, and the working temperature of each zone is: first zone 150-160°C, the second zone is 165~175°C, the third zone is 165~175°C, and the fourth zone is 170~180°C.
PCT/CN2014/070594 2013-09-30 2014-01-14 Zero halogen sheath material for 125°c irradiation cross-linked epcv photovoltaics, and method for preparation thereof WO2015043122A1 (en)

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