CN104151693A - Nuclear electric cable insulation material and preparation method thereof - Google Patents
Nuclear electric cable insulation material and preparation method thereof Download PDFInfo
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- 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
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- 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
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- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
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- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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Abstract
The present invention relates to a nuclear electric cable insulation material, which comprises a low VA content ethylene-vinyl acetate copolymer, a high VA content ethylene-vinyl acetate copolymer, a polyolefin graft, a fire retardation agent, a cross-linking sensitizer, a plasticizer, an antioxidant, an anti-aging agent, a vulcanizing agent, an accelerator, a coloring agent, and a processing aid. The preparation method comprises: mixing the weighed raw materials and stirring, carrying out extruding granulating through a twin-screw extruder, carrying out plasticizing sheet-forming of the granulated granules through an open mill, placing the obtained sheet material in a hydraulic press, and carrying out irradiation cross-linking on the obtained sample sheet to obtain the cross-linked nuclear electric cable insulation material with characteristics of oil resistance, acid resistance, freezing resistance and low temperature resistance. The nuclear electric cable insulation material of the present invention has characteristics of excellent oil resistance, excellent acid resistance, excellent low temperature resistance, low embrittlement temperature of less than -45 DEG C, excellent fire retardation, high oxygen index of more than 40%, good combustion self-extinguishing property, excellent mechanical performance, and excellent electrical property, wherein each performance achieves the balanced state.
Description
Technical field
The invention belongs to electric wire and cable material field, the one specifically providing mainly for nuclear industry industry is for nuclear cables insulating material and preparation method thereof.
Background technology
In recent years, along with the great attention of country to environmental protection, there is severe weather in some big and medium-sized cities, the whole nation particularly continuously, the people's quality of life and life security are had a strong impact on, therefore national proposition will be greatly developed nuclear electricity, reduce coal fired power generation amount, utilize clean energy to substitute traditional thermal power generation, conscientiously transform mode of economic growth.Because Nuclear power plants electric wire used is had relatively high expectations, generally all adopt at present fireproofing cable material without halide, therefore the demand of fireproofing cable material without halide was increased fast at these several years, and according to Chinese cable system statistics, only the output of annual non-halogen flame-retardant cable in 2013 has just exceeded 100,000 tons.
Obtain rapid growth in non-halogen flame-retardant cable output in, performance and range of application to its product are also had higher requirement.As nuclear cables, high ferro locomotive cable, shipboard cable etc. for ocean, not only requiring is low-smoke non-halogen flame-retardant, it must be also oil resistant, acidproof, antifreeze anti-low temperature etc., could meet service requirements, and conventional fireproofing cable material without halide in the market, at oil resistant, acidproof, in antifreeze cryophylactic performance index, exist much contradiction, oil resistant, acidproof index reaches, and antifreeze anti-low temperature index does not reach, or antifreeze anti-low temperature index reaches, and oil resistant, acidproof index can't pass, this is also to produce at present the ubiquitous technical problem of nuclear cables CABLE MATERIALS enterprise.
The polymkeric substance that more current enterprises manufacture halogen-free flameproof material adopts polyolefine material mostly, and especially taking ethylene-vinyl acetate copolymer (EVA) as main, its advantage one is that price comparison is low; The 2nd, technological operation is easy; The 3rd, when the flame-proof material making burns, the amount of being fuming is low, and toxicity is little.But oil-proofness is poor, and a little less than mineral filler bonding force, be its main drawback.
The oil resistance of EVA is relevant to the content of VA, and the content of VA is higher, and oil-proofness is better, but resistance to low temperature and mechanical property can decrease.And can well improve lower temperature resistance by adding softening agent, just in the mechanical property of material, can decrease.Simultaneously, mostly conventional fireproofing cable material without halide is to adopt the inorganic fire-retarded systems such as magnesium hydroxide, aluminium hydroxide at present, this flame-retardant system is mainly to decompose by fire retardant, absorb heat and discharge water outlet simultaneously, reach fire-retardant object, due to its burning crust poor-performing, thereby self-extinguishing can be poor.Therefore at present in the urgent need to by technological innovation, solve for the insulation material technology technical problem of using on nuclear cables.
Summary of the invention
Goal of the invention: the object of the invention is in order to overcome deficiency of the prior art, provide a kind of for nuclear cables insulating material and preparation method thereof, this material has excellent oil resistance acid resistance, comprise resistance to mineral oil and oil fuel performance, excellent resistance to low temperature, embrittlement temperature is lower than-45 DEG C, excellent flame retardant properties, its oxygen index is more than 40%, low smoke performance (nonflame smoke density is less than or equal to 350), and there is good burning self-extinguishing energy, and mechanical property (more than tensile elongation 13MPa) and electrical property are good, and each performance reaches balance.
Technical scheme: in order to solve the problems of the technologies described above, one of the present invention is for nuclear cables insulating material, it comprises the raw material of following weight percentage,
In the ethylene-vinyl acetate copolymer of described low VA content, VA weight percentage is 10-25%, can improve the mechanical property of CABLE MATERIALS; In the ethylene-vinyl acetate copolymer of described high VA content, VA weight percentage is 40-60%, can improve the oil resistance of CABLE MATERIALS; Described Graft Polyolefin is maleic anhydride stem grafting polyolefin, as maleic anhydride graft Low Density Polyethylene, maleated ethylene vinyl acetate copolyme etc., can improve the cohesive action between matrix resin and fire retardant, improves mechanical property; Described crosslinking sensitizer is multi-functional esters of acrylic acid; Described fire retardant is the composite mixture being made up of A and B, and described A adopts tricresyl phosphate second fat, and described B adopts stannous octoate; Described promotor is N, the two thiamides of N-tetramethyl-two sulphur (being called for short TMTD); Described softening agent is dioctyl sebacate (DOS) or Octyl adipate (DOA), can improve the resistance to low temperature of CABLE MATERIALS; Described oxidation inhibitor is phenolic antioxidant, amine antioxidants or phosphite ester kind antioxidant.
Described crosslinking sensitizer is that multi-functional esters of acrylic acid is trimethylolpropane trimethacrylate (TMPTMA), Viscoat 295 (TMPTA), triallylcyanurate (TAC) or TAIC etc., and crosslinking sensitizer can reduce the required absorption dose of cross-linking radiation; Described vulcanizing agent is 2,5-dimethyl-2,5-bis(t-butylperoxy) hexane (being called for short DBPMH).
Described processing aid is one or more in Zinic stearas, paraffin and silicone oil; Described anti-aging agent is 2-mercaptobenzimidazole (being called for short MB), and described tinting material is carbon black.
Described oxidation inhibitor is selected phenolic antioxidant, as antioxidant 1010, antioxidant 1076 etc., amine antioxidants, as oxidation inhibitor 4010, oxidation inhibitor N, N-bis-(betanaphthyl) Ursol D (DNP) etc., and phosphite ester kind antioxidant, described phosphite ester kind antioxidant is as irgasfos 168 etc.
For a preparation method for nuclear cables Insulation Material, it comprises the steps,
(1), according to the preparation method of nuclear cables Insulation Material, its feed composition and corresponding weight percentage take raw material;
(2) raw material taking being first placed in to high-speed stirring closes machine and carries out after mix and blend, carry out extruding pelletization three times through twin screw extruder again, the sum velocity that stirs that described high-speed stirring is closed machine is 1000-1200rpm, in described twin screw extruder from feeding section each section of extruder temperature, as be respectively: 130 DEG C, 135 DEG C, 120 DEG C, 135 DEG C, 145 DEG C, 128 DEG C, 130 DEG C, 135 DEG C, 140 DEG C;
(3) pellet after granulation is plastified in mill, slice, the temperature of described mill is 100-130 DEG C;
(4) sheet stock of acquisition is placed in to hydropress and first adopts pressurization preheating 5-8 hour, then pressurized, heated, then after the cooling 2-4 of pressurize hour to room temperature, obtain test piece;
(5) test piece of acquisition is carried out to cross-linking radiation, obtain described crosslinked oil resistant, acidproof, antifreeze anti-low temperature modification nuclear cables insulating material, wherein irradiation dose is 17-20Mrad.
In described step (2), described churning time is 3-6 hour, and the temperature in described twin screw extruder is 130-160 DEG C; In described step (4), the temperature of described hydropress is 160-180 DEG C, and the pressure of hydropress pressurization is not less than 15Mpa, and the described pressurized, heated time is 4-8 hour.
Described cross-linking radiation design adopts machinery electronic integral accelerator to carry out.
Beneficial effect: the present invention compared with prior art, its remarkable advantage is: the present invention has excellent oil resistance acid resistance, comprise resistance to mineral oil and oil fuel performance, excellent resistance to low temperature, embrittlement temperature is lower than-45 DEG C, excellent flame retardant properties, its oxygen index is more than 40%, low smoke performance (nonflame smoke density is less than or equal to 350), and there is good burning self-extinguishing energy, and mechanical property (more than tensile elongation 13MPa) and electrical property are good, and each performance reaches balance, preparation method of the present invention selects suitable matrix resin, Graft Polyolefin, fire retardant, softening agent, antioxidant, crosslinking sensitizer, vulcanizing agent, promotor, processing aid and tinting material, and the appropriate proportioning of raw material, not only there is relative equilibrium and excellent mechanical property, oil resistant acid resistance, resistance to low temperature, low smoke performance, but also there is the performances such as unique flame retardant properties, fire-retardant burning self-extinguishing energy and effect are fairly obvious.
Embodiment
Below by embodiment, the present invention is further illustrated.
Embodiment 1:
For a preparation method for nuclear cables Insulation Material, it comprises the steps,
(1), according to as in table 1 embodiment 1, its feed composition and corresponding weight percentage take raw material;
(2) raw material taking is first placed in to high-speed stirring and closes machine and carry out mix and blend after 6 hours, then carry out extruding pelletization three times through twin screw extruder; The sum velocity that stirs that described high-speed stirring is closed machine is 900rpm; In described twin screw extruder from feeding section each section of extruder temperature, as be respectively: 130 DEG C, 135 DEG C, 120 DEG C, 135 DEG C, 145 DEG C, 128 DEG C, 130 DEG C, 135 DEG C, 140 DEG C;
(3) pellet after granulation is plastified in mill, slice, the temperature of described mill is 100 DEG C;
(4) sheet stock of acquisition is placed in to hydropress and first adopts pressurization preheating 5 hours, then pressurized, heated is 5 hours, then pressurize, to room temperature after cooling 2 hours, obtains just expecting, obtains test piece; The temperature of described hydropress is 150 DEG C, and the pressure of hydropress pressurization is not less than 16Mpa.
(5) test piece of acquisition is carried out to cross-linking radiation, obtain described crosslinked oil resistant, acidproof, antifreeze anti-low temperature modification nuclear cables insulating material, wherein irradiation dose is 17Mrad.
The one of embodiment 1 gained is carried out to the detections such as mechanical property, oil resistant acid resistance, cold resistance energy, electrical property, flame retardant properties, the results of property of the performance of resulting materials as shown in embodiment in table 21 for nuclear cables Insulation Material material.Can obtain this material from the performance data of gained and there is acidproof, the anti-low temperature of excellent oil resistant, low smoke performance and flame retardant properties, and mechanical property, electrical property are all very good.
Embodiment 2:
A kind of preparation method for nuclear cables Insulation Material of the present embodiment, it comprises the steps,
(1), according to as in embodiment in table 12, its feed composition and corresponding weight percentage take raw material;
(2) raw material taking is first placed in to high-speed stirring and closes machine and carry out mix and blend after 5 hours, then carry out extruding pelletization three times through twin screw extruder; The sum velocity that stirs that described high-speed stirring is closed machine is 1000rpm.In described twin screw extruder from feeding section each section of extruder temperature, as be respectively: 120 DEG C, 125 DEG C, 130 DEG C, 130 DEG C, 135 DEG C, 135 DEG C, 140 DEG C, 135 DEG C, 130 DEG C.
(3) pellet after granulation is plastified in mill, slice, the temperature of described mill is 120 DEG C;
(4) sheet stock of acquisition is placed in to hydropress and first adopts pressurization preheating 6 hours, then pressurized, heated is 6 hours, then pressurize, to room temperature after cooling 3 hours, obtains just expecting, obtains test piece; The temperature of described hydropress is 160 DEG C, and the pressure of hydropress pressurization is not less than 17Mpa.
(5) test piece of acquisition is carried out to cross-linking radiation, obtain described crosslinked oil resistant, acidproof, antifreeze anti-low temperature modification nuclear cables insulating material, wherein irradiation dose is 18Mrad.
The one of embodiment 2 gained is carried out to the detections such as mechanical property, oil resistant acid resistance, cold resistance energy, electrical property, flame retardant properties, the results of property of the performance of resulting materials as shown in embodiment in table 21 for nuclear cables Insulation Material material.Can obtain this material from the performance data of gained and there is acidproof, the anti-low temperature of excellent oil resistant, low smoke performance and flame retardant properties, and mechanical property, electrical property are all very good.
Embodiment 3:
A kind of preparation method for nuclear cables Insulation Material of the present embodiment, it comprises the steps,
(1), according to as in embodiment in table 13, its feed composition and corresponding weight percentage take raw material;
(2) raw material taking is first placed in to high-speed stirring and closes machine and carry out mix and blend after 4 hours, then carry out extruding pelletization three times through twin screw extruder; The sum velocity that stirs that described high-speed stirring is closed machine is 850rpm.In described twin screw extruder from feeding section each section of extruder temperature, as be respectively: 110 DEG C, 115 DEG C, 120 DEG C, 120 DEG C, 125 DEG C, 120 DEG C, 130 DEG C, 125 DEG C, 125 DEG C.
(3) pellet after granulation is plastified in mill, slice, the temperature of described mill is 110 DEG C;
(4) sheet stock of acquisition is placed in to hydropress and first adopts pressurization preheating 7 hours, then pressurized, heated is 7 hours, then pressurize, to room temperature after cooling 3 hours, obtains just expecting, obtains test piece; The temperature of described hydropress is 150 DEG C, and the pressure of hydropress pressurization is not less than 18Mpa.
(5) test piece of acquisition is carried out to cross-linking radiation, obtain described crosslinked oil resistant, acidproof, antifreeze anti-low temperature modification nuclear cables insulating material, wherein irradiation dose is 19Mrad.
The one of embodiment 3 gained is carried out to the detections such as mechanical property, oil resistant acid resistance, cold resistance energy, electrical property, flame retardant properties, the results of property of the performance of resulting materials as shown in embodiment in table 21 for nuclear cables Insulation Material material.Can obtain this material from the performance data of gained and there is acidproof, the anti-low temperature of excellent oil resistant, low smoke performance and flame retardant properties, and mechanical property, electrical property are all very good.
The proportioning raw materials of table 1 embodiment 1-3
The performance of table 2 embodiment 1-3 resulting materials
Claims (5)
1. for a nuclear cables Insulation Material, it is characterized in that: it comprises the raw material of following weight percentage,
In the ethylene-vinyl acetate copolymer of described low VA content, VA weight percentage is 10-25%; In the ethylene-vinyl acetate copolymer of described high VA content, VA weight percentage is 40-60%; Described Graft Polyolefin is maleic anhydride stem grafting polyolefin, and described crosslinking sensitizer is multi-functional esters of acrylic acid; Described fire retardant is the composite mixture being made up of A and B, and described A adopts tricresyl phosphate second fat, and described B adopts stannous octoate; Described promotor is N, the two thiamides of N-tetramethyl-two sulphur; Described softening agent is dioctyl sebacate or Octyl adipate; Described oxidation inhibitor is phenolic antioxidant, amine antioxidants or phosphite ester kind antioxidant.
2. one according to claim 1, for nuclear cables Insulation Material, is characterized in that: described crosslinking sensitizer is that multi-functional esters of acrylic acid is TMPTMA, TMPTA, TAIC or TAC; Described vulcanizing agent is 2,5-dimethyl-2,5-bis(t-butylperoxy) hexane.
3. one according to claim 1, for nuclear cables Insulation Material, is characterized in that: described processing aid is one or more in Zinic stearas, paraffin and silicone oil; Described anti-aging agent is 2-mercaptobenzimidazole, and described tinting material is carbon black.
4. according to the arbitrary described a kind of preparation method for nuclear cables Insulation Material of claim 1-3, it is characterized in that: it comprises the steps,
(1), according to the preparation method of nuclear cables Insulation Material, its feed composition and corresponding weight percentage take raw material;
(2) raw material taking is first placed in to high-speed stirring and closes machine and carry out after mix and blend, then carry out extruding pelletization three times through twin screw extruder;
(3) pellet after granulation is plastified in mill, slice, the temperature of described mill is 100-130 DEG C;
(4) sheet stock of acquisition is placed in to hydropress and first adopts pressurization preheating 5-8 hour, then pressurized, heated, then after the cooling 2-4 of pressurize hour to room temperature, obtain test piece;
(5) test piece of acquisition is carried out to cross-linking radiation, obtain described crosslinked oil resistant, acidproof, antifreeze anti-low temperature modification nuclear cables insulating material, wherein irradiation dose is 17-20Mrad.
5. a kind of preparation method for nuclear cables Insulation Material according to claim 4, is characterized in that: in described step (2), described churning time is 3-6 hour, and the temperature in described twin screw extruder is 130-160 DEG C; In described step (4), the temperature of described hydropress is 160-180 DEG C, and the pressure of hydropress pressurization is not less than 15Mpa, and the described pressurized, heated time is 4-8 hour.
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Cited By (6)
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| CN105273297A (en) * | 2015-11-17 | 2016-01-27 | 中广核三角洲（江苏）塑化有限公司 | Tear-resistant, high-strength, low-smoke, halogen-free and flame-retardant cable sheath material and preparation technology thereof |
| CN108485142A (en) * | 2018-02-27 | 2018-09-04 | 重庆鸽牌电线电缆有限公司 | A kind of cable for rolling stock of EVM and EPDM rubbers compound inslation |
| CN109575418A (en) * | 2018-12-10 | 2019-04-05 | 中广核三角洲（苏州）高聚物有限公司 | 105 DEG C of oil-resisting type irradiated crosslinking low-smoke and halogen-free flame retardant CABLE MATERIALSs and preparation method thereof |
| CN111710464A (en) * | 2020-07-10 | 2020-09-25 | 无锡市华美电缆有限公司 | High-temperature-resistant high-voltage cable and preparation method thereof |
| CN112409678A (en) * | 2020-11-06 | 2021-02-26 | 远东电缆有限公司 | Low-smoke halogen-free sheath material for wind power cable |
| CN116120653A (en) * | 2021-11-12 | 2023-05-16 | 南京喜悦科技股份有限公司 | Oil-resistant halogen-free red phosphorus-free flame-retardant polyolefin heat-shrinkable material and heat-shrinkable tube prepared from same |
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| CN105273297A (en) * | 2015-11-17 | 2016-01-27 | 中广核三角洲（江苏）塑化有限公司 | Tear-resistant, high-strength, low-smoke, halogen-free and flame-retardant cable sheath material and preparation technology thereof |
| CN105273297B (en) * | 2015-11-17 | 2017-12-15 | 中广核三角洲（江苏）塑化有限公司 | Tear-proof high-strength low-smoke halogen-free flame-proof cable sheath material and its preparation technology |
| CN108485142A (en) * | 2018-02-27 | 2018-09-04 | 重庆鸽牌电线电缆有限公司 | A kind of cable for rolling stock of EVM and EPDM rubbers compound inslation |
| CN109575418A (en) * | 2018-12-10 | 2019-04-05 | 中广核三角洲（苏州）高聚物有限公司 | 105 DEG C of oil-resisting type irradiated crosslinking low-smoke and halogen-free flame retardant CABLE MATERIALSs and preparation method thereof |
| CN111710464A (en) * | 2020-07-10 | 2020-09-25 | 无锡市华美电缆有限公司 | High-temperature-resistant high-voltage cable and preparation method thereof |
| CN111710464B (en) * | 2020-07-10 | 2022-02-18 | 无锡市华美电缆有限公司 | High-temperature-resistant high-voltage cable and preparation method thereof |
| CN112409678A (en) * | 2020-11-06 | 2021-02-26 | 远东电缆有限公司 | Low-smoke halogen-free sheath material for wind power cable |
| CN116120653A (en) * | 2021-11-12 | 2023-05-16 | 南京喜悦科技股份有限公司 | Oil-resistant halogen-free red phosphorus-free flame-retardant polyolefin heat-shrinkable material and heat-shrinkable tube prepared from same |
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Application publication date: 20141119 |