CN114456475A - Low-smoke halogen-free material for nuclear power station cable and preparation method thereof - Google Patents
Low-smoke halogen-free material for nuclear power station cable and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 80
- 239000000779 smoke Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title abstract description 18
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 22
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 17
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims abstract description 15
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims abstract description 15
- 239000000347 magnesium hydroxide Substances 0.000 claims abstract description 15
- 239000006057 Non-nutritive feed additive Substances 0.000 claims abstract description 11
- VSVVZZQIUJXYQA-UHFFFAOYSA-N [3-(3-dodecylsulfanylpropanoyloxy)-2,2-bis(3-dodecylsulfanylpropanoyloxymethyl)propyl] 3-dodecylsulfanylpropanoate Chemical compound CCCCCCCCCCCCSCCC(=O)OCC(COC(=O)CCSCCCCCCCCCCCC)(COC(=O)CCSCCCCCCCCCCCC)COC(=O)CCSCCCCCCCCCCCC VSVVZZQIUJXYQA-UHFFFAOYSA-N 0.000 claims abstract description 11
- -1 divinyl aluminum Chemical compound 0.000 claims abstract description 11
- 229910001377 aluminum hypophosphite Inorganic materials 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims description 49
- 238000001035 drying Methods 0.000 claims description 25
- 229910052736 halogen Inorganic materials 0.000 claims description 19
- 238000005469 granulation Methods 0.000 claims description 18
- 230000003179 granulation Effects 0.000 claims description 18
- 150000002367 halogens Chemical class 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 9
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 8
- 229920002379 silicone rubber Polymers 0.000 claims description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
- 239000005977 Ethylene Substances 0.000 claims description 5
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 2
- 238000004132 cross linking Methods 0.000 claims description 2
- 238000010894 electron beam technology Methods 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims description 2
- 230000001737 promoting effect Effects 0.000 claims 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 9
- 239000003063 flame retardant Substances 0.000 abstract description 9
- 230000005855 radiation Effects 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 238000012545 processing Methods 0.000 abstract description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 7
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 239000004594 Masterbatch (MB) Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 3
- 239000004945 silicone rubber Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- MFLXFWVWEPHGMZ-UHFFFAOYSA-K tris[bis(ethenyl)phosphoryloxy]alumane Chemical compound C(=C)P(=O)([O-])C=C.[Al+3].C(=C)P(=O)([O-])C=C.C(=C)P(=O)([O-])C=C MFLXFWVWEPHGMZ-UHFFFAOYSA-K 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000003878 thermal aging Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- XKIVKIIBCJIWNU-UHFFFAOYSA-N o-[3-pentadecanethioyloxy-2,2-bis(pentadecanethioyloxymethyl)propyl] pentadecanethioate Chemical compound CCCCCCCCCCCCCCC(=S)OCC(COC(=S)CCCCCCCCCCCCCC)(COC(=S)CCCCCCCCCCCCCC)COC(=S)CCCCCCCCCCCCCC XKIVKIIBCJIWNU-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/002—Methods
- B29B7/005—Methods for mixing in batches
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
- H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
Abstract
The invention belongs to the technical field of cable materials, and relates to a low-smoke halogen-free material for a nuclear power station cable and a preparation method thereof. The raw materials for preparing the low-smoke halogen-free material comprise the following components in parts by weight: 100 parts of ethylene-vinyl acetate copolymer, 80-95 parts of magnesium hydroxide, 15-20 parts of divinyl aluminum hypophosphite, 20-30 parts of antimony trioxide, 10-15 parts of compatilizer, 1-2.5 parts of Revonox 501, 1-2.5 parts of pentaerythritol tetrakis (3-lauryl thiopropionate), 0.5-1.5 parts of 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate, 1-1.5 parts of sensitizer and 0.5-1 part of processing aid. The low-smoke halogen-free material for the nuclear power station cable and the preparation method thereof can be used for preparing the low-smoke halogen-free material for the nuclear power station cable, the prepared low-smoke halogen-free material has good mechanical and processing properties, good flame retardant effect and radiation resistance, and the service life can be as long as more than 80 years, so that the use of the 1E-grade nuclear power station cable is met.
Description
Technical Field
The invention belongs to the technical field of cable materials, and relates to a low-smoke halogen-free material for a nuclear power station cable and a preparation method thereof.
Background
The nuclear safety-grade cables of the Hualong I nuclear power station are designed according to 60 years, and the Hualong subsequent model research and development project provides a new requirement for the 80-year design life of the nuclear power station.
The nuclear safety cables of the nuclear power station are numerous, huge manpower and material resources can be wasted when the nuclear safety cables are laid again, and related projects such as fireproof plugging and the like also need to be constructed again. The cables used in the nuclear power station are heavy and may need some equipment to complete the related laying work, and the local area of the cable laying path may be quite narrow and the equipment cannot enter. Once the cabling of the nuclear power plant is completed, it is difficult to re-lay and parts of the area are areas where personnel are strictly prohibited to access, which makes cable replacement difficult or even impossible. In addition, the nuclear power station has a large number of cables and a bridge has limited available capacity, and new cables are difficult to add without dismantling the original cables. Therefore, in order to meet the requirement of the 80-year design life of the Hualong follow-up type nuclear power plant and meet new environmental conditions, it is necessary to develop a nuclear safety grade cable which meets the new requirement and can reach the 80-year design life.
The class 1E cables for nuclear power plants (definition of class 1E: safety class of electrical system equipment that performs the functions of containment isolation, emergency cooling of reactor core, removal of residual heat from reactor, removal of heat from containment vessel, and prevention of radioactive emission to the surrounding environment) are classified into three categories according to the safety category of electrical system equipment of nuclear power plants: k1, K2 and K3.
Low smoke, halogen free and flame retardant are the basic requirements of cables for nuclear power stations, because a halogen containing system generates a large amount of black smoke and acid mist during combustion, and secondary pollution is generated. These fumes are sufficient to suffocate people and cause the breakdown of vital equipment (e.g., computers, etc.) due to corrosion.
Therefore, designing halogen-free flame-retardant wire and cable products meeting the requirements of low smoke, low toxicity and low corrosion becomes an urgent task in the nuclear power field.
Disclosure of Invention
The invention aims to provide a low-smoke halogen-free material for a nuclear power station cable, which has good mechanical and processing properties, good flame retardant effect and radiation resistance, and a service life of over 80 years, so that the use of the nuclear power station cable of the 1E grade is met.
In order to achieve the purpose, in a basic embodiment, the invention provides a low-smoke halogen-free material for a nuclear power station cable, which comprises the following raw materials in parts by weight: 100 parts of ethylene-vinyl acetate copolymer, 80-95 parts of magnesium hydroxide, 15-20 parts of divinyl aluminum hypophosphite, 20-30 parts of antimony trioxide, 10-15 parts of compatilizer, 1-2.5 parts of Revonox 501, 1-2.5 parts of pentaerythritol tetrakis (3-lauryl thiopropionate), 0.5-1.5 parts of 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate, 1-1.5 parts of sensitizer and 0.5-1 part of processing aid.
In a preferred embodiment, the invention provides a low smoke zero halogen material for a cable of a nuclear power station, wherein the melt index of the ethylene-vinyl acetate copolymer is 2-5g/10min, and the molar ratio of ethylene to vinyl acetate is 4: 1-1.56.
In a preferred embodiment, the invention provides a low smoke zero halogen material for cables of nuclear power plants, wherein the compatilizer is used for increasing the compatibility of ethylene-vinyl acetate copolymer with magnesium hydroxide, divinyl aluminum hypophosphite and antimony trioxide, and is selected from maleic anhydride grafted ethylene-vinyl acetate copolymer or carboxylic acid grafted ethylene-vinyl acetate copolymer.
In a preferred embodiment, the present invention provides a low smoke zero halogen material for nuclear power plant cables, wherein the sensitizer is used to promote the crosslinking of the low smoke zero halogen material when irradiated by electron beams, and is selected from triallyl isocyanurate or trimethylolpropane trimethacrylate.
In a preferred embodiment, the invention provides a low smoke zero halogen material for a nuclear power station cable, wherein the processing aid is used for preventing the low smoke zero halogen material from sticking to the wall at high temperature, and is selected from silicone rubber or silicone master batch.
The second purpose of the invention is to provide a preparation method of the low-smoke halogen-free material for the nuclear power station cable, so that the low-smoke halogen-free material can be better prepared, the prepared low-smoke halogen-free material has good mechanical and processing properties, good flame retardant effect and radiation resistance, and the service life can be as long as more than 80 years, thereby meeting the use requirement of the 1E grade nuclear power station cable.
In order to achieve the purpose, in a basic embodiment, the invention provides a preparation method of the low-smoke halogen-free material for the cable of the nuclear power station, which comprises the following steps:
(1) fully mixing the raw materials except the processing aid according to the formula amount;
(2) mixing the mixed raw materials, adding a processing aid in a formula amount in the process, and then granulating, drying and cooling;
(3) and mixing, granulating and drying the cooled material again.
In a preferred embodiment, the invention provides a method for preparing the low smoke zero halogen material for the cable of the nuclear power station, wherein in the step (1), the mixing comprises mixing the ethylene-vinyl acetate copolymer and the compatilizer in a first mixer, mixing the magnesium hydroxide, the divinyl aluminum hypophosphite and the antimony trioxide in a second mixer, and mixing the Revonox 501, the pentaerythritol tetrakis (3-lauryl thiopropionate), the n-octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and the sensitizer in a third mixer, wherein the mixing time in each mixer is 1-2 minutes independently.
In a preferred embodiment, the invention provides a preparation method of the low-smoke zero-halogen material for the cable of the nuclear power station, wherein in the step (2), the mixed raw materials are transferred to an internal mixer, the processing aid is added at 90 ℃, and the materials are transferred to a double screw for granulation after reaching 130 ℃.
In a preferred embodiment, the invention provides a method for preparing the low-smoke halogen-free material for the cable of the nuclear power station, wherein in the step (2) and the step (3),
the temperature of the feeding section of the double-screw granulation is 90-105 ℃, the temperature of the conveying section is 110-,
the drying temperature is 40-50 ℃, the drying time is 1-3 hours,
the cooling is carried out for 16-40 hours after the temperature is cooled to 10-25 ℃.
In a preferred embodiment, the invention provides a preparation method of the low smoke zero halogen material for the cable of the nuclear power station, wherein in the step (3), the mixing is carried out in an internal mixer, the mixing temperature is 130-140 ℃, and the mixing time is 12-15 min.
The low-smoke halogen-free material for the nuclear power station cable and the preparation method thereof have the advantages that the low-smoke halogen-free material for the nuclear power station cable can be prepared, the prepared low-smoke halogen-free material has good mechanical and processing properties, good flame retardant effect and radiation resistance, and the service life can be as long as more than 80 years, so that the use of the 1E-grade nuclear power station cable is met.
The low-smoke halogen-free material for the nuclear power station cable and the preparation method thereof have the beneficial effects that:
(1) the material has long service life: the material is selected from antimony trioxide (Sb)2O3) Compared with the prior nuclear power cable material added with a large amount of aluminum hydroxide and magnesium hydroxide, the flame retardant system has the advantages of very small addition amount and relatively large resin content, thereby greatly prolonging the thermal aging life of the material. In addition, the material is compounded by three antioxidants of pentaerythritol tetra (3-lauryl thiopropionate), Revonox 501 (lactone antioxidant) and n-octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, so that a synergistic effect can be achieved, a long-term protection effect can be formed on the material, and the heat aging life of the material is prolonged. In addition, the material preparation method adopts a secondary mixing process, namely, the secondary mixing granulation is carried out after the primary mixing granulation is finished and the cooling is carried out for 16 hours, compared with the prior art, the technology has great advantages, and can lead various components of the material to be dispersed more uniformly, thereby prolonging the thermal aging life of the material.
(2) Excellent radiation resistance of the material: in the prior art, polyimide or cerium oxide and the like are used as radiation-resistant agents, so that on one hand, the raw materials are extremely high in price, and on the other hand, the raw materials have great damage to the mechanical properties of the materials, so that the extrusion performance is poor; the invention adopts the synergy of the high gel content, the composite antioxidant and the antimony trioxide, thereby playing a role in resisting radiation, being capable of withstanding the irradiation with the dose of 2300kGy, and simultaneously having lower material cost and excellent mechanical property.
(3) Low corrosivity of the material: the material of the invention does not generate corrosive gas such as hydrogen halide when burned, thereby not endangering the life health of people or causing corrosive damage to machine equipment.
(4) The material has excellent flame retardant property: the magnesium hydroxide, the divinyl aluminum phosphate and the antimony trioxide can greatly endow the material with excellent flame retardant property, can increase the carbon forming amount of the material during combustion, and can effectively prevent the dripping phenomenon of the material during combustion. In addition, even if the cable is in a bundled state, the fire can not spread, and the requirements of international standards such as IEC332-3/IEEE-383 and the like can be met.
Detailed Description
The following examples are provided to further illustrate the embodiments of the present invention.
Example 1: preparation of low-smoke halogen-free material for nuclear power station cable
The raw materials for preparing the low-smoke halogen-free material for the nuclear power station cable in the embodiment are as follows: 100Kg of ethylene-vinyl acetate copolymer (melt index of 2g/10min, molar ratio of ethylene to vinyl acetate of 4:1), 85Kg of magnesium hydroxide, 16Kg of aluminum divinylhypophosphite, 25Kg of antimony trioxide, 12Kg of compatibilizer (maleic anhydride grafted ethylene-vinyl acetate copolymer), 5011.2 Kg of Revonox, 1.2Kg of pentaerythritol tetrakis (3-laurylthiopropionate), 0.7Kg of n-octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 1.2Kg of triallyl isocyanurate, and 0.5Kg of silicone rubber (morning glowing).
The specific preparation process comprises the following steps:
(1) mixing ethylene-vinyl acetate copolymer and compatibilizer at normal temperature in a first mixer (SHR-300L, Leyu mechanical plant, Zhang Home, City), mixing magnesium hydroxide, aluminum divinyl hypophosphite and antimony trioxide at normal temperature in a second mixer (SHR-300L, Leyu-Kong mechanical factory), revonox 501, pentaerythritol tetrakis (3-laurylthiopropionate), n-octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and triallyl isocyanurate were mixed at normal temperature in a third mixer (SHR-25L, Leyu mechanical plant, Zhanghong Kong) for 1 minute (mixing speed 200 rpm), then the materials mixed in the three mixers are transferred into the first mixer to be mixed for 1 minute at normal temperature (the mixing and stirring speed is 200 r/min).
(2) Transferring the mixed raw materials into an internal mixer, adding silicon rubber at 90 ℃, transferring the materials into a double screw for granulation after the temperature reaches 130 ℃, wherein the temperature of a feeding section of the double screw granulation is 90 ℃, the temperature of a conveying section is 125 ℃, the temperature of a melting section is 145 ℃, and the temperature of a machine head is 150 ℃. Drying and cooling after granulation, wherein the drying temperature is 40 ℃ and the drying time is 2 hours; the cooling was carried out to 15 ℃ and then the temperature was maintained for 16 hours.
(3) Mixing, granulating and drying the cooled material again, wherein the mixing is carried out in an internal mixer, the mixing temperature is 135 ℃, and the mixing time is 12 min; the temperature of a feeding section of the double-screw granulation is 90 ℃, the temperature of a conveying section is 125 ℃, the temperature of a melting section is 145 ℃, and the temperature of a machine head is 150 ℃; the drying temperature was 40 ℃ and the drying time was 2 hours.
Example 2: preparation of low-smoke halogen-free material for nuclear power station cable
The raw materials for preparing the low-smoke halogen-free material for the nuclear power station cable in the embodiment are as follows: 100Kg of ethylene-vinyl acetate copolymer (melt index of 4g/10min, molar ratio of ethylene to vinyl acetate 4:1.56), 95Kg of magnesium hydroxide, 15Kg of aluminum divinylhypophosphite, 25Kg of antimony trioxide, 15Kg of compatibilizer (carboxylic acid grafted ethylene-vinyl acetate copolymer), 5011.5 Kg of Revonox, 1.5Kg of pentaerythritol tetrakis (3-laurylthiopropionate), 0.9Kg of n-octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 1.5Kg of triallyl isocyanurate, and 0.5Kg of silicone master batch (Dow Corning).
The specific preparation process comprises the following steps:
(1) mixing ethylene-vinyl acetate copolymer and compatibilizer at normal temperature in a first mixer (SHR-300L, Leyu mechanical plant, Zhang Home, City), mixing magnesium hydroxide, aluminum divinyl hypophosphite and antimony trioxide at normal temperature in a second mixer (SHR-300L, Leyu-Kong mechanical factory), revonox 501, pentaerythritol tetrakis (3-laurylthiopropionate), n-octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and triallyl isocyanurate were mixed at normal temperature in a third mixer (SHR-25L, Leyu mechanical plant, Zhanghong Kong) for 1 minute (mixing speed 200 rpm), then the materials mixed in the three mixers are transferred into the first mixer to be mixed for 1 minute at normal temperature (the mixing and stirring speed is 200 r/min).
(2) Transferring the mixed raw materials into an internal mixer, adding silicone master batch at 90 ℃, transferring the materials into a double screw for granulation after the temperature reaches 130 ℃, wherein the temperature of a feeding section of the double screw granulation is 90 ℃, the temperature of a conveying section is 125 ℃, the temperature of a melting section is 145 ℃, and the temperature of a machine head is 150 ℃. Drying and cooling after granulation, wherein the drying temperature is 45 ℃ and the drying time is 1.5 hours; the cooling was carried out for 16 hours after cooling to 25 ℃.
(3) Mixing the cooled materials again, granulating and drying, wherein the mixing is carried out in an internal mixer, the mixing temperature is 135 ℃, and the mixing time is 14 min; the temperature of a feeding section of the double-screw granulation is 90 ℃, the temperature of a conveying section is 125 ℃, the temperature of a melting section is 145 ℃, and the temperature of a machine head is 150 ℃; the temperature of drying was 45 ℃ and the time was 2.5 hours.
Example 3: preparation of low-smoke halogen-free material for nuclear power station cable
The raw materials for preparing the low-smoke halogen-free material for the nuclear power station cable in the embodiment are as follows: 100Kg of ethylene-vinyl acetate copolymer (melt index of 5g/10min, molar ratio of ethylene to vinyl acetate of 4:1), 90Kg of magnesium hydroxide, 18Kg of aluminum divinylhypophosphite, 28Kg of antimony trioxide, 13Kg of compatibilizer (carboxylic acid grafted ethylene-vinyl acetate copolymer), 5011.3 Kg of Revonox, 1.3Kg of pentaerythritol tetrakis (3-laurylthiopropionate), 0.8Kg of n-octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 1.3Kg of triallyl isocyanurate, and 0.5Kg of silicone rubber (morning vulcanization).
The specific preparation process comprises the following steps:
(1) mixing ethylene-vinyl acetate copolymer and compatibilizer at normal temperature in a first mixer (SHR-300L, Leyu mechanical plant, Zhang Home, City), mixing magnesium hydroxide, aluminum divinyl hypophosphite and antimony trioxide at normal temperature in a second mixer (SHR-300L, Leyu-Kong mechanical factory), revonox 501, pentaerythritol tetrakis (3-laurylthiopropionate), n-octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and triallyl isocyanurate were mixed at normal temperature in a third mixer (SHR-25L, Leyu mechanical plant, Zhanghong Kong) for 1 minute (mixing speed 200 rpm), then the materials mixed in the three mixers are transferred into the first mixer to be mixed for 1 minute at normal temperature (the mixing and stirring speed is 200 r/min).
(2) Transferring the mixed raw materials into an internal mixer, adding silicon rubber at 90 ℃, transferring the materials into a double screw for granulation after the temperature reaches 130 ℃, wherein the temperature of a feeding section of the double screw granulation is 90 ℃, the temperature of a conveying section is 125 ℃, the temperature of a melting section is 145 ℃, and the temperature of a machine head is 150 ℃. Drying and cooling after granulation, wherein the drying temperature is 50 ℃ and the drying time is 1 hour; the cooling was carried out to 25 ℃ and then the temperature was maintained for 20 hours.
(3) Mixing, granulating and drying the cooled material again, wherein the mixing is carried out in an internal mixer, the mixing temperature is 135 ℃, and the mixing time is 15 min; the temperature of a feeding section of the double-screw granulation is 90 ℃, the temperature of a conveying section is 125 ℃, the temperature of a melting section is 145 ℃, and the temperature of a machine head is 150 ℃; the drying temperature was 50 ℃ and the drying time was 2 hours.
Example 4: examples 1-3 Performance testing of Low Smoke zero halogen materials
The low smoke zero halogen materials prepared in examples 1-3 were tested for their performance, and the methods and results are shown in Table 1 below.
Table 1 method and results for testing the performance of low smoke zero halogen materials prepared in examples 1-3
The above-described embodiments are merely illustrative of the present invention, which may be embodied in other specific forms or in other specific forms without departing from the spirit or essential characteristics thereof. The described embodiments are, therefore, to be considered in all respects as illustrative and not restrictive. The scope of the invention should be indicated by the appended claims, and any changes that are equivalent to the intent and scope of the claims should be construed to be included therein.
Claims (10)
1. The low-smoke halogen-free material for the cable of the nuclear power station is characterized by comprising the following raw materials in parts by weight: 100 parts of ethylene-vinyl acetate copolymer, 80-95 parts of magnesium hydroxide, 15-20 parts of divinyl aluminum hypophosphite, 20-30 parts of antimony trioxide, 10-15 parts of compatilizer, 1-2.5 parts of Revonox 501, 1-2.5 parts of pentaerythritol tetrakis (3-lauryl thiopropionate), 0.5-1.5 parts of 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate, 1-1.5 parts of sensitizer and 0.5-1 part of processing aid.
2. The low smoke zero halogen material of claim 1, characterized in that: the melt index of the ethylene-vinyl acetate copolymer is 2-5g/10min, wherein the molar ratio of ethylene to vinyl acetate is 4: 1-1.56.
3. The low smoke zero halogen material of claim 1, characterized in that: the compatilizer is used for increasing the compatibility of the ethylene-vinyl acetate copolymer with magnesium hydroxide, divinyl aluminum hypophosphite and antimony trioxide, and is selected from maleic anhydride grafted ethylene-vinyl acetate copolymer or carboxylic acid grafted ethylene-vinyl acetate copolymer.
4. The low smoke zero halogen material of claim 1, characterized in that: the sensitizer is used for promoting the crosslinking of the low-smoke halogen-free material under the irradiation of electron beams and is selected from triallyl isocyanurate or trimethylolpropane trimethacrylate.
5. The low smoke zero halogen material of claim 1, characterized in that: the processing aid is used for preventing the low-smoke halogen-free material from being stained on the wall at high temperature, and is selected from silicon rubber or silicone master batches.
6. A method for preparing a low smoke zero halogen material according to any of claims 1 to 5, characterized in that said method comprises the following steps:
(1) fully mixing the raw materials except the processing aid according to the formula amount;
(2) mixing the mixed raw materials, adding a processing aid in a formula amount in the process, and then granulating, drying and cooling;
(3) and mixing, granulating and drying the cooled material again.
7. The method of claim 6, wherein: in the step (1), the mixing comprises the steps of mixing an ethylene-vinyl acetate copolymer and a compatilizer in a first mixer, mixing magnesium hydroxide, divinyl aluminum hypophosphite and antimony trioxide in a second mixer, and mixing Revonox 501, pentaerythritol tetrakis (3-lauryl thiopropionate), n-octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and a sensitizer in a third mixer, wherein the mixing time in each mixer is 1-2 minutes independently.
8. The method according to claim 6, wherein in the step (2), the mixed raw materials are transferred to an internal mixer, the processing aid is added at 90 ℃, and the materials are transferred to a twin screw for granulation after reaching 130 ℃.
9. The method of claim 8, wherein: in the step (2) and the step (3),
the temperature of the feeding section of the double-screw granulation is 90-105 ℃, the temperature of the conveying section is 110-,
the drying temperature is 40-50 ℃, the drying time is 1-3 hours,
the cooling is carried out for 16-40 hours after the temperature is cooled to 10-25 ℃.
10. The method of claim 6, wherein: in the step (3), the mixing is carried out in an internal mixer, the mixing temperature is 130-140 ℃, and the mixing time is 12-15 min.
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