CN102108148B - Irradiation-crosslinked low-smoke halogen-free inflaming retarding insulation material for nuclear power station cable and preparation method thereof - Google Patents
Irradiation-crosslinked low-smoke halogen-free inflaming retarding insulation material for nuclear power station cable and preparation method thereof Download PDFInfo
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- CN102108148B CN102108148B CN2010106194106A CN201010619410A CN102108148B CN 102108148 B CN102108148 B CN 102108148B CN 2010106194106 A CN2010106194106 A CN 2010106194106A CN 201010619410 A CN201010619410 A CN 201010619410A CN 102108148 B CN102108148 B CN 102108148B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
- B29C48/875—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling for achieving a non-uniform temperature distribution, e.g. using barrels having both cooling and heating zones
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92904—Die; Nozzle zone
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- Engineering & Computer Science (AREA)
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- Thermal Sciences (AREA)
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Abstract
The invention provides an irradiation-crosslinked low-smoke halogen-free inflaming retarding insulation material for a nuclear power station cable. The insulation material comprises the following components in parts by weight: 100 parts of basic resin (A), 2-5 parts of antioxidant (B), 3-10 parts of irradiation-resisting agent (C), 110-170 parts of fire retardant (D), 2-10 parts of compatilizer (E), 0.1-0.8 part of anticopper agent (F), 0.2-2 parts of lubricant (G) and 2-10 parts of cross-linking sensitizing agent (H), wherein the basic resin (A) comprises a combination of polyethylene-octeneelastomer (POE) ethylene-butyl acrylate (EBA) and linear very low density polyethylene (VLDPE), and the weight ratio of the POE to the EBA to the VLDPE is (10-20):(65-80):(10-20).
Description
Technical field
The present invention relates to a kind of irradiated crosslinking low-smoke halogen-free flame-retardant isolating material and preparation method, be specifically related to a kind of cables of nuclear power with 1E grade irradiation crosslinking low-smoke halogen-free flame-retardant isolating material and preparation method.
Background technology
Used in nuclear power station 1E level cable should be Halogen, low cigarette, low toxicity, flame retardant cable, and cable has superior anti-secular heat aging performance, electric stability, chemicalstability and radioresistance.Cable insulation material commonly used is under the environment of long term heat ageing and radioprotective, and it is serious that degraded takes place polymkeric substance, and the performance of material can not satisfy the request for utilization of cables of nuclear power.Third generation cables of nuclear power requires under 90 ℃ service condition now, and will surpass 60 years work-ing life, and the design service life of original cable material is about 40 years.The life-time service life-span of cable material has much room for improvement.
In addition, the cable that is installed in the nuclear power plant containment shell is under the radiation regimes for a long time, and in order to guarantee the normal use of cable, cable material must possess good capability of resistance to radiation.Conventional oxidation inhibitor is obvious inadequately to the radiation resistance of polymer materials, and prior art adopts inorganic anti irradiation agent and rare earth organic compounds.The rare earth organism costs an arm and a leg, the adding of inorganic anti irradiation agent is very big to the mechanical property influence of material.
In sum, but this area lacks a kind ofly can satisfy irradiated crosslinking low-smoke halogen-free flame-retardant isolating material and the cable that above-mentioned over-all properties requires.
For this reason, this area presses for a kind of deficiency that overcomes prior art, and anti-long term heat ageing property is superior, and cable material is under 90 ℃ service condition, and surpass 60 years work-ing life, cable insulating material for power station that anti-irradiation ability is strong and preparation method.
Summary of the invention
First purpose of the present invention is to obtain a kind of deficiency that overcomes prior art, and anti-long term heat ageing property is superior, and cable material is under 90 ℃ service condition, and surpass 60 years work-ing life, the cable insulating material for power station that anti-irradiation ability is strong.
Second purpose of the present invention is to obtain a kind of deficiency that overcomes prior art, and anti-long term heat ageing property is superior, and cable material is under 90 ℃ service condition, and surpass 60 years work-ing life, the used in nuclear power station cable that anti-irradiation ability is strong.
The 3rd purpose of the present invention is to provide a kind of deficiency that overcomes prior art, and anti-long term heat ageing property is superior, and cable material is under 90 ℃ service condition, and surpass 60 years work-ing life, the preparation method of the cable insulating material for power station that anti-irradiation ability is strong.
In first aspect of the present invention, but a kind of irradiated crosslinking low-smoke halogen-free flame-retardant isolating material that can be used for cables of nuclear power is provided, has it is characterized in that said Insulation Material comprises following components by weight percent:
(A) base resin is 100 parts;
(B) oxidation inhibitor is 2～5 parts;
(C) anti-irradiation agent is 3～10 parts;
(D) fire retardant is 110～170 parts;
(E) compatilizer is 2～10 parts;
(F) anti copper agent is 0.1～0.8 part;
(G) lubricant is 0.2～2 part
(H) crosslinking sensitizer is 2～10 parts;
The base resin of said component (A) comprises following component: ethylene-octene copolymer (POE), ethylene-propylene acid butyl ester (EBA) and line style ultra-low density polyethylene (VLDPE) three's combination, and three's weight ratio is followed successively by (10～20): (65～80): (10～20).
In an embodiment of the present invention, the melting index of said ethylene-octene (POE) multipolymer is: 1～6g/10min; Perhaps
The melting index of said ethylene-propylene acid butyl ester (EBA) multipolymer is: 0.5～5g/10min, and wherein the quality percentage composition of Bing Xisuandingzhi is: 10～30%, with ethylene-propylene acid butyl ester (EBA) multipolymer total weight; Perhaps
The melting index of said line style ultra-low density polyethylene (VLDPE) is: 0.5～5g/10min.
In an embodiment of the present invention; Described oxidation inhibitor is 4; 4 '-two (propyloxy phenyl base) pentanoic (Naugard445), four [3-(3; The 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010), β, β '-sulfuration dipropionic acid SUNSOFT Q-182S (PS802) or its combination;
Preferably, said oxidation inhibitor is 4,4 '-two (propyloxy phenyl base) pentanoic: antioxidant 1010: β, and the combination of β '-sulfuration dipropionic acid SUNSOFT Q-182S, its weight ratio is (0.5～2.5) in regular turn: (0.5～1.5): (1～1.5).
In an embodiment of the present invention, described anti-irradiation agent is zinc salt of 2 mercaptobenzimidazole (MBZ), 2,2,4 trimethyl 1,2 dihydroquinoline polymer (RD) or its combination;
Preferably, said antiradiation agent is zinc salt of 2 mercaptobenzimidazole and 2,2,4 trimethyl 1,2 dihydroquinoline polymer combination, and its weight ratio is (1～6) in regular turn: (2～4).
In an embodiment of the present invention, described fire retardant is an inorganic combustion inhibitor; Be preferably oxyhydroxide, melamine class and boratory combination; More preferably be that described fire retardant is the combination of Marinco H, trimeric cyanamide, zinc borate; Most preferably, the weight ratio of said Marinco H, trimeric cyanamide and zinc borate is (95～150): (5～15): (5～15).
In an embodiment of the present invention, described compatilizer is the grafted maleic anhydride multipolymer of ethene or its multipolymer;
Preferably, described compatilizer is ethylene-octene copolymer grafted maleic anhydride multipolymer or ethene grafted maleic anhydride multipolymer.
In an embodiment of the present invention, described anti copper agent is N, N '-two [β (3, the 5-di-tert-butyl-hydroxy phenyl) propionyl] hydrazine, two [ethyl-3-(3, the 5-di-tert-butyl-hydroxy phenyl)] 2,2 '-oxamide or its combination;
More preferably, anti copper agent is the Irganox MD-1024 of Switzerland's vapour crust.
In an embodiment of the present invention, described lubricant is calcium stearate, Zinic stearas, Magnesium Stearate, polyethylene wax or its combination; Perhaps
Described crosslinking sensitizer is triallyl isocyanurate (TAIC) or trihydroxy methyl propane trimethyl acrylate.
But second purpose of the present invention is to obtain the said cables of nuclear power that irradiated crosslinking low-smoke halogen-free flame-retardant isolating material of the present invention obtains.
But the 3rd purpose of the present invention is to obtain the preparation method of described irradiated crosslinking low-smoke halogen-free flame-retardant isolating material, and described preparation method may further comprise the steps:
With the fire retardant of component (D) mixed to temperature to 110 ℃ ± 5 ℃ proportionally, add and stir discharging in 3～6 minutes behind the lubricant of component (G) and place, with other components by the proportioning extruding pelletization, but obtain described irradiated crosslinking low-smoke halogen-free flame-retardant isolating material;
Preferably, used dual-screw pelletizer among the described preparation method, four temperature sections in the extruding pelletization process are: 115～125 ℃ of feeding sections, 125～135 ℃ of transportation sections, 135～145 ℃ of melt zones, 140～150 ℃ of heads.
In a preference; The fire retardant of component (D) proportionally is blended in the high-speed mixer high speed is mixed to temperature to 110 ℃ ± 5 ℃; Stir discharging in 3～6 minutes placement after adding Zinic stearas; Use double-screw extruding pelletizing machine extruding pelletization with unclassified stores by proportioning, but promptly obtain used in nuclear power station irradiated crosslinking low-smoke halogen-free flame-retardant isolating material.
Embodiment
The inventor is through extensive and deep research; Through adopting new base resin; It is superior to have obtained a kind of anti-long term heat ageing property; Cable material surpasses 60 years (prior art is generally 40 years), cable insulating material for power station that anti-irradiation ability is strong and preparation method work-ing life under 90 ℃ service condition.In a preference, adopted specific auxiliary agent, can be so that the mechanical property of Insulation Material, anti-radiation performance, various over-all propertieies of life-span descend; Also can adopt specific fire retardant to obtain the prescription of high flame retardant simultaneously, be specially adapted to cables of nuclear power.Accomplished the present invention on this basis.
The implication of " Halogen " of the present invention, " low cigarette " can be referring to the performance index of this area used in nuclear power station 1E level cable.Used in nuclear power station 1E level cable should be Halogen, low cigarette, low toxicity, flame retardant cable, and cable has superior anti-secular heat aging performance, electric stability, chemicalstability and radioresistance.
Below detail to various aspects of the present invention:
Specify like nothing, various raw materials of the present invention all can obtain through commercially available; Or prepare according to the ordinary method of this area.Only if definition or explanation are arranged in addition, the same meaning that all specialties used herein and scientific words and those skilled in the art are familiar with.Any in addition with the institute similar content of putting down in writing or the equalization method and material all can be applicable in the inventive method.
Component of insulation material for nuclear power plant cable and preparation method thereof
Above-mentioned technical purpose of the present invention is able to implement through following technical scheme: cables of nuclear power is used the irradiated crosslinking low-smoke halogen-free flame-retardant isolating material, and the weight part of each component title and each component is:
100 parts of base resins;
2～5 parts in oxidation inhibitor;
3～10 parts of anti-irradiation agent;
110～170 parts of fire retardants;
2～10 parts of compatilizers;
0.1～0.8 part of anti copper agent;
0.2～2 part of lubricant;
2～10 parts of crosslinking sensitizers.
Said Insulation Material randomly can also contain the component of this area Insulation Material commonly used, the not concrete restriction of these components, only otherwise goal of the invention of the present invention is produced restriction to get final product.
The invention solves the existing cable material and be lower than the difficult problem in 60 years 90 ℃ of life-time service life-spans.
Base resin
Base resin of the present invention adopts: the mixture of ethylene-octene (POE) multipolymer, ethylene-propylene acid butyl ester (EBA), the ultra dense degree Vilaterm of line style (VLDPE), therein ethylene-octene (POE) multipolymer are commonly used in the prior art.Must contain the ethylene-propylene acid butyl ester in the base resin of the present invention, more preferably cooperate to make to be higher than the cable material in 60 years 90 ℃ of life-time service life-spans with the ultra dense degree Vilaterm of line style (VLDPE).Wherein, the ethylene-propylene acid butyl ester has excellent thermotolerance, radiation resistance, can significantly improve the work-ing life of material; The ultra dense degree Vilaterm of line style (VLDPE) has high tensile strength, fabulous snappiness, anti-chemical and radiation resistance; The two cooperates with ethylene-octene (POE) multipolymer and has obtained good performance.
Particularly, the requirement of said ethylene-octene (POE) multipolymer is: melting index is: 1～6g/10min.Ethylene-propylene acid butyl ester (EBA) multipolymer requires: melting index is: 0.5～5g/10min, and wherein the quality percentage composition of Bing Xisuandingzhi is: 10～30%, with said multipolymer total weight.The melting index of the ultra dense degree Vilaterm of line style (VLDPE) is: 0.5～5g/10min.
Said ethylene-octene (POE) multipolymer, ethylene-propylene acid butyl ester (EBA), the ultra dense degree Vilaterm of line style (VLDPE) are the commercially available product that gets.
Oxidation inhibitor
Described oxidation inhibitor is selected from: 4; 4 '-two (propyloxy phenyl base) pentanoic (Naugard445), four [3-(3; The 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010), β, β '-sulfuration dipropionic acid SUNSOFT Q-182S (PS802) or its combination.
The contriver finds; Amine antioxidants 4; 4 '-two (propyloxy phenyl base) pentanoic can have remarkable thermostability and long-acting resistant to thermal aging performance when being used for prescription of the present invention, merge with hindered phenol antioxygen 1010 and use the long-term heat aging property that can effectively improve material.For this reason; The contriver provides a preferred implementation; Wherein said oxidation inhibitor is 4,4 '-two (propyloxy phenyl base) pentanoic (Naugard445), four [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010), β; The combination of β '-sulfuration dipropionic acid SUNSOFT Q-182S (PS802); And 4,4 '-two (propyloxy phenyl base) pentanoic wherein: antioxidant 1010: β, the weight ratio of β '-sulfuration dipropionic acid SUNSOFT Q-182S is (0.5～2.5) in regular turn: (0.5～1.5): (1～1.5).
Said oxidation inhibitor is the commercially available product that gets.
Anti-irradiation agent
The inventor finds, zinc salt of 2 mercaptobenzimidazole, 2,2; 4-trimethylammonium-1; 2-EEDQ polymkeric substance is used in has good radiation resistance in the polymkeric substance of the present invention, the advantage of resistant to thermal aging is arranged simultaneously, and more crucial is; Compare with the agent of inorganic anti irradiation, little to the mechanical property influence of cable material.For this reason, described anti-irradiation agent of the present invention preferably is selected from: the combination of zinc salt of 2 mercaptobenzimidazole (MBZ), 2,2,4 trimethyl 1,2 dihydroquinoline polymer (RD).
Described anti-irradiation agent is the commercially available product that gets, and for example anti-irradiation agent zinc salt of 2 mercaptobenzimidazole is the MBZ of Dunhuang Chenical Plant, Shanghai; 2,2,4 trimethyl 1,2 dihydroquinoline polymer (RD) is produced for Jiangsu Sheng'Ao Chemical Technology Co., Ltd.
Fire retardant
The cables of nuclear power insulated wire cores requires through single testing vertical flammability, and in the prior art, product adding inorganic combustion inhibitor reaches fire-retardant purpose usually, has reduced the mechanical property and the electric stability of material.And it is relatively more difficult through single testing vertical flammability.
For this reason, the applicant provides the combination of inorganic combustion inhibitor and organic fire-retardant; Preferably, described fire retardant is selected from: the combination of Marinco H, melamine class, zinc borate.The heat decomposition temperature of trimeric cyanamide is greater than 300 ℃, and thermal endothermic decomposition is trimeric cyanamide and cyanuric acid, dilution oxygen and inflammable gas.In the use, the addition of trimeric cyanamide is few, and is very little to the mechanical property influence of material.Do not have water clock during burning, cooperate with Marinco H to have good flame retardant resistance.This insulating material has radiation resistance, and insulated wire cores can be passed through single testing vertical flammability, and preparation technology is simple.
The trimeric cyanamide based flame retardant is known to those skilled in the art, comprises trimeric cyanamide and trimeric cyanamide salt thereof or its condenses (for example with the condenses of aldehydes, for example the condenses of formaldehyde).Said trimeric cyanamide salt can be commercially available salts such as urine cyanate.
Compatilizer
Compatilizer of the present invention need improve the dispersiveness of inorganic combustion inhibitor in resin, and improves the mechanical property of material.
Particularly, compatilizer of the present invention can be the grafted maleic anhydride multipolymer compatilizer of ethene or its multipolymer.
Preferably, the described compatilizer of the present invention's use is selected from: a kind of (the Injecatable EVA Copolymer grafted maleic anhydride) in ethylene-octene copolymer grafted maleic anhydride multipolymer (POE-g-MAH) or the ethene grafted maleic anhydride multipolymer (PE-g-MAH).Said compatilizer can significantly improve the dispersiveness of inorganic combustion inhibitor in resin, and improves the mechanical property of material, and does not influence other performances.
More preferably, compatilizer is an ethylene-octene copolymer grafted maleic anhydride multipolymer (POE-g-MAH).
Anti copper agent
Anti copper agent of the present invention need have the heavy metal ion of inhibition catalysis aged ability.Described anti copper agent is selected from: N, and N '-two [β (3, the 5-di-tert-butyl-hydroxy phenyl) propionyl] hydrazine (MD1024), anti-copper evil effect is remarkable, and has with resin compatible well, and good dispersivity has antioxygen and anti-copper dual function.
Preferred anti copper agent is the Irganox MD-1024 of Switzerland's vapour crust.A kind of in addition anti copper agent: two [ethyl-3-(3; The 5-di-tert-butyl-hydroxy phenyl)] 2; 2 '-oxamide also is
XL-1-is this to be of little use.
Lubricant
Described lubricant is a kind of of calcium stearate, Zinic stearas, Magnesium Stearate or polyethylene wax or combination.
Crosslinking sensitizer
Described crosslinking sensitizer is a kind of in triallyl isocyanurate (TAIC), the trihydroxy methyl propane trimethyl acrylate.
Preferred, said crosslinking sensitizer reaches the TAIC crosslinking sensitizer of chemical ltd for Shanghai Fang Rui.
The preparation method of halogen-free flame retardant insulation material
Among the present invention, cables of nuclear power may further comprise the steps with the preparation method of irradiated crosslinking low-smoke halogen-free flame-retardant isolating material:
Fire retardant proportionally is blended in the high-speed mixer high speed is mixed to temperature to 110 ℃ ± 5 ℃; Stir discharging in 3～6 minutes placement after adding Zinic stearas; Use double-screw extruding pelletizing machine extruding pelletization with unclassified stores by proportioning, but promptly obtain cables of nuclear power with the irradiated crosslinking low-smoke halogen-free flame-retardant isolating material.
Preferably, used dual-screw pelletizer, four temperature sections in the extruding pelletization process are: 115～125 ℃ of feeding sections, 125～135 ℃ of transportation sections, 135～145 ℃ of melt zones, 140～150 ℃ of heads.
Preferred, above-mentioned double-screw extruding pelletizing machine is that Nanjing Rhea polymkeric substance equipment ltd produces.
Cables of nuclear power and preparation method thereof
Insulation Material of the present invention is processed behind the sample cable that can obtain used in nuclear power station through cross-linking radiation.Said cross-linking radiation is the ordinary skill in the art, is known to those skilled in the art.
Concrete for example the employing electron accelerator irradiation is crosslinked, and irradiation dose is 12Mrad～15Mrad.
Cables of nuclear power of the present invention has following advantage with irradiated crosslinking low-smoke halogen-free flame-retardant isolating material and preparation method:
These product performance satisfy the requirement of used in nuclear power station 1E level cable fully, and product is in the leading level in the world.
Be in particular in:
1. this product is selected the mixture of ethylene-octene (POE) multipolymer, ethylene-propylene acid butyl ester (EBA), the ultra dense degree Vilaterm of line style (VLDPE) for use; Selected special antioxidant system for use; Product has good long-term resistance to heat aging, and the work-ing life of material was above 60 years;
2. excellent anti-radiation performance satisfies in the nuclear power plant containment shell under the harsh nuclear radiation environment fully, and cable is kept the operation of normal function.
3. the insulated wire cores that insulating material of the present invention is made can be through single vertical combustion examination (GB/T18380.12-2008)
Insulation Material of the present invention is when the insulation layer of preparation cables of nuclear power, and crosslinked through the rumbatron realization, production technique is simple, energy consumption is low.
Other aspects of the present invention are because the disclosure of this paper is conspicuous to those skilled in the art.
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in the restriction scope of the present invention.The experimental technique of unreceipted actual conditions in the following example is measured according to national standard usually.If there is not a corresponding national standards, then carry out according to general international standard, normal condition or according to the condition that manufacturer advises.Unless otherwise indicated, otherwise all umbers are weight part, and all per-cents are weight percentage.
Only if definition or explanation are arranged in addition, the same meaning that all specialties used herein and scientific words and those skilled in the art are familiar with.Any in addition with the institute similar content of putting down in writing or the equalization method and material all can be applicable in the inventive method.
Embodiment 1
Each component title and each composition weight umber are following:
EBA 70Kg
POE 20Kg
VLDPE 10Kg
Mg(OH)
2 110Kg
Trimeric cyanamide 15Kg
Zinc borate 5Kg
Compatilizer (POE-g-MAH) 4Kg
Naugard?445 1Kg
Irganox?1010 0.5Kg
PS802 1.5Kg
Zinc salt of 2 mercaptobenzimidazole (MBZ) 3Kg
2,2,4 trimethyl 1,2 dihydroquinoline polymer (RD) 2Kg
Irganox?MD-1024 0.3Kg
Zinic stearas 0.5Kg
Triallyl isocyanurate (TAIC) 4Kg
The preparation method of foregoing invention; It comprises following process step: fire retardant magnesium hydroxide, trimeric cyanamide, zinc borate are mixed to temperature to 110 ℃ ± 5 ℃ according to proportioning in the high-speed mixer high speed; Stir discharging in 3～6 minutes placement after adding Zinic stearas, use dual-screw pelletizer (Nanjing Rhea polymkeric substance equipment ltd produces) extruding pelletization by proportioning with unclassified stores.Four temperature sections in the extruding pelletization process are: 115～125 ℃ of feeding sections, 125～135 ℃ of transportation sections, 135～145 ℃ of melt zones, 140～150 ℃ of heads.Insulation Material is processed behind the sample crosslinked through electron accelerator irradiation, and irradiation dose is 12Mrad～15Mrad.
Product among the embodiment 1 is carried out the Performance Detection test, and each performance numerical value is shown in performance embodiment.
Embodiment 2
Each component title and each composition weight umber are following:
EBA 65Kg
POE 20Kg
VLDPE 15Kg
Mg(OH)
2 95Kg
Trimeric cyanamide 5Kg
Zinc borate (ZnB) 10Kg
Compatilizer (POE-g-MAH) 2Kg
Naugard?445 0.5Kg
Irganox?1010 0.5Kg
PS802 1Kg
Zinc salt of 2 mercaptobenzimidazole (MBZ) 1Kg
2,2,4 trimethyl 1,2 dihydroquinoline polymer (RD) 2Kg
Irganox?MD-1024 0.1Kg
Zinic stearas 0.2Kg
Triallyl isocyanurate (TAIC) 2Kg
The preparation method of above-mentioned CABLE MATERIALS is identical with embodiment 1
Product among the embodiment 2 is carried out the Performance Detection test, and each performance numerical value is shown in performance embodiment.
Embodiment 3.
Each component title and each composition weight umber are following:
EBA 70Kg
POE 15Kg
VLDPE 15Kg
Mg(OH)
2 125Kg
Trimeric cyanamide 10Kg
Zinc borate (ZnB) 15Kg
Compatilizer (POE-g-MAH) 6Kg
Naugard?445 1.5Kg
Irganox?1010 1.2Kg
PS802 1.3Kg
Zinc salt of 2 mercaptobenzimidazole (MBZ) 5Kg
2,2,4 trimethyl 1,2 dihydroquinoline polymer (RD) 2Kg
Irganox?MD-1024 0.5Kg
Zinic stearas 1Kg
Triallyl isocyanurate (TAIC) 6Kg
The preparation method of above-mentioned CABLE MATERIALS is identical with embodiment 1.
Product among the embodiment 3 is carried out the Performance Detection test, and each performance numerical value is shown in performance embodiment.
Embodiment 4.
Each component title and each composition weight umber are following:
EBA 70Kg
POE 10Kg
VLDPE 20Kg
Mg(OH)
2 150Kg
Trimeric cyanamide 10Kg
Zinc borate (ZnB) 10Kg
Compatilizer (POE-g-MAH) 10Kg
Naugard?445 2.5Kg
Irganox?1010 1.5Kg
PS802 1Kg
Zinc salt of 2 mercaptobenzimidazole (MBZ) 6Kg
2,2,4 trimethyl 1,2 dihydroquinoline polymer (RD) 4Kg
Irganox?MD-1024 0.8Kg
Zinic stearas 2Kg
Triallyl isocyanurate (TAIC) 10Kg
The preparation method of above-mentioned CABLE MATERIALS is identical with embodiment 1.
Product among the embodiment 4 is carried out the Performance Detection test, and each performance numerical value is shown in performance embodiment.
Performance embodiment
Table 1 embodiment 1 product performance test result
" * "The present invention confirms the aging resistance of cable through simulated experiment.Be equivalent to the test and assess elongation at break loss of material of 150 ℃ of x 30 60 year work-ing life all over the world and be not higher than 50%.The also available American I EEE383 standard of the present invention, the accelerating thermal aging test condition: 138 ℃ of x300h, be equivalent to 40 years work-ing life of material, wherein the elongation at break loss is not higher than 50%.Through evaluation and test, aging resistance of the present invention reaches necessary requirement (60 years).
All the other embodiment values of touching the mark.
The above is merely preferred embodiment of the present invention; Be not in order to limit essence technology contents scope of the present invention; Essence technology contents of the present invention is broadly to be defined in the claim scope of application, and if any technological entity or method that other people accomplish are defined identical with the claim scope of application; Also or a kind of change of equivalence, all will be regarded as and be covered by among this claim scope.
All documents in that the present invention mentions are all quoted as a reference in this application, are just quoted such as a reference separately as each piece document.Should be understood that in addition that after having read foregoing of the present invention those skilled in the art can do various changes or modification to the present invention, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Claims (12)
1. but irradiated crosslinking low-smoke halogen-free flame-retardant isolating material that can be used for cables of nuclear power is characterized in that said Insulation Material comprises following components by weight percent:
(A) base resin is 100 parts;
(B) oxidation inhibitor is 2～5 parts;
Described oxidation inhibitor is 4,4 '-two (propyloxy phenyl base) pentanoic (Naugard445), four [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010), β, β '-sulfuration dipropionic acid SUNSOFT Q-182S (PS802) or its combination;
(C) anti-irradiation agent is 3～10 parts;
Described anti-irradiation agent is zinc salt of 2 mercaptobenzimidazole (MBZ), 2,2,4 trimethyl 1,2 dihydroquinoline polymer (RD) or its combination;
(D) fire retardant is 110～170 parts;
Described fire retardant is inorganic combustion inhibitor and organic fire-retardant combination; Be in particular oxyhydroxide, melamine class and boratory combination;
(E) compatilizer is 2～10 parts;
(F) anti copper agent is 0.1～0.8 part;
(G) lubricant is 0.2～2 part;
(H) crosslinking sensitizer is 2～10 parts;
The base resin of said component (A) comprises following component: ethylene-octene copolymer (POE), ethylene-propylene acid butyl ester (EBA) and line style ultra-low density polyethylene (VLDPE) three's combination, and three's weight ratio is followed successively by (10～20): (65～80): (10～20).
2. Insulation Material as claimed in claim 1 is characterized in that,
Said oxidation inhibitor is 4,4 '-two (propyloxy phenyl base) pentanoic, antioxidant 1010, β, the combination of β '-sulfuration dipropionic acid SUNSOFT Q-182S, and its weight ratio is (0.5～2.5) in regular turn: (0.5～1.5): (1～1.5).
3. Insulation Material as claimed in claim 1 is characterized in that, said antiradiation agent is zinc salt of 2 mercaptobenzimidazole and 2,2,4 trimethyl 1,2 dihydroquinoline polymer combination, and its weight ratio is (1～6) in regular turn: (2～4).
4. Insulation Material as claimed in claim 1 is characterized in that, described fire retardant is the combination of Marinco H, trimeric cyanamide, zinc borate, and the weight ratio of said Marinco H, trimeric cyanamide and zinc borate is (95～150): (5～15): (5～15).
5. Insulation Material as claimed in claim 1 is characterized in that, described compatilizer is the grafted maleic anhydride multipolymer of ethene or its multipolymer.
6. Insulation Material as claimed in claim 1 is characterized in that, described compatilizer is an ethylene-octene copolymer grafted maleic anhydride multipolymer.
7. Insulation Material as claimed in claim 1 is characterized in that, described anti copper agent is N, N '-two [β (3, the 5-di-tert-butyl-hydroxy phenyl) propionyl] hydrazine, two [ethyl-3-(3, the 5-di-tert-butyl-hydroxy phenyl)] 2,2 '-oxamide or its combination.
8. Insulation Material as claimed in claim 1 is characterized in that, anti copper agent is the Irganox MD-1024 of Switzerland's vapour crust.
9. Insulation Material as claimed in claim 1 is characterized in that,
Described lubricant is calcium stearate, Zinic stearas, Magnesium Stearate, polyethylene wax or its combination; Perhaps
Described crosslinking sensitizer is triallyl isocyanurate (TAIC) or trihydroxy methyl propane trimethyl acrylate.
10. but cables of nuclear power that obtains like the described irradiated crosslinking low-smoke halogen-free flame-retardant isolating material of arbitrary claim in the claim 1～9.
11. but the preparation method like the described irradiated crosslinking low-smoke halogen-free flame-retardant isolating material of arbitrary claim in the claim 1～9, it is characterized in that: described preparation method may further comprise the steps:
The fire retardant of component (D) proportionally is mixed to temperature to 110 ℃ ± 5 ℃, adds and stir discharging in 3～6 minutes behind the lubricant of component (G) and place, with other components by the proportioning extruding pelletization, but obtain described irradiated crosslinking low-smoke halogen-free flame-retardant isolating material.
12. method as claimed in claim 11 is characterized in that, used dual-screw pelletizer among the described preparation method; Four temperature sections in the extruding pelletization process are: 115～125 ℃ of feeding sections; 125～135 ℃ of transportation sections, 135～145 ℃ of melt zones, 140～150 ℃ of heads.
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