CN105462083A - 1E-grade K1 type thermal shrinkage electrical stress control tube for nuclear power station and preparation method of 1E-grade K1 type thermal shrinkage electrical stress control tube - Google Patents
1E-grade K1 type thermal shrinkage electrical stress control tube for nuclear power station and preparation method of 1E-grade K1 type thermal shrinkage electrical stress control tube Download PDFInfo
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- 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
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D23/00—Producing tubular articles
- B29D23/001—Pipes; Pipe joints
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- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- 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
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
- C08L2312/06—Crosslinking by radiation
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Abstract
The invention provides a 1E-grade K1 type thermal shrinkage electrical stress control tube which is prepared from, by weight, 70-100 parts of crystalline ethylene-propylene-diene monomer, 0-30 parts of polyethylene, 10-30 parts of modified barium titanate, 20-40 parts of high-abrasion-resistant carbon black, 2-5 parts of a sensitizing agent, 2-4 parts of an anti-aging agent, 5-10 parts of a radiation-hardened agent and 2-4 parts of a lubricating agent. The 1E-grade K1 type thermal shrinkage electrical stress control tube for the nuclear power station is resistant to thermal aging, resistant to radiation and good in electric stress control effect and can be used as a thermal shrinkage electrical stress control material in a radiation-resistant thermal shrinkage cable accessory for the 1E-grade K1 type nuclear power station.
Description
Technical field
The present invention relates to a kind of used in nuclear power station thermal contraction electric stress control tube and preparation method thereof.
Background technology
Nuclear energy has become the important energy source that the mankind use, and nuclear energy power generation is the important component part of power industry.Because nuclear power can not cause the pollution to air, more and more pay attention to the situation of global greenhouse effect, climate change people under, actively push forward Construction of Nuclear Electricity, important policies of China's energy construction, for meeting economy and the ever-increasing energy demand of social development, promote China's synthesized economic strength, industrial technology level and international status, all have great importance.
Within 2007, " national nuclear power developing special topic planning (2005-2020) " is mentioned, and runs installed capacity and strives for reaching 4,000 ten thousand kilowatts, and continue after having 1,800 ten thousand kilowatts of projects in construction to carry over the year two thousand twenty to the year two thousand twenty nuclear power.The proportion that nuclear power accounts for whole electric power installed capacity brings up to 4% from less than 2%, and nuclear power annual electricity generating capacity reaches 2600 ~ 2,800 hundred million kilowatt-hours.In the year being Chinese Nuclear Power and restarting for 2015, also put nuclear power generating sets into commercial operation maximum 1 year by becoming China, the work-ing life extending Nuclear power plants is the long-term goal of economic construction.
Nuclear power plants life-time dilatation, this just requires that the materials'use life-spans such as the cable of coupling and cable accessory use 40 years from original 90 DEG C of temperature condition, directly brings up to use 60 years.And also must meet as the thermal contraction electric stress control material of the core component of middle high-pressure cable accessory the performance requriements using 60 years (heat-proof aging, radiation hardness) at 90 DEG C of temperature condition.Thermal contraction electric stress control tube is the core component of middle high-pressure cable accessory, situation can be concentrated by the electric field stress of at all releiving in cable accessory terminal and intermediate head, homogenize electric field distribution, reduce the probability of electrical breakdown, improve middle high-pressure nuclear power cable, or even Nuclear power plants reliability of operation and security.
Used in nuclear power station 1E level K1 class thermal contraction electric stress controls material and use 60 years under 90 DEG C of temperature condition, requires all to meet following performance:
(1) under normal temperature time (23 ± 2 DEG C): tensile strength>=9.0MPa; Elongation at break>=250%; Volume specific resistance>=1.0 × 10
9Ω .cm, <1.0 × 10
13Ω .cm; Specific inductivity>=25; Dielectric loss value≤0.8;
After the thermal ageing of (2) 175 DEG C, 230 hours: tensile strength>=7MPa, elongation at break>=100%; Volume specific resistance>=1.0 × 10
9Ω .cm, <1.0 × 10
13Ω .cm; Specific inductivity>=15; Dielectric loss value≤0.8;
(3) 175 DEG C, 230 h heat aging time, after radiation dose 2400KGy: tensile strength>=5.5Mpa; Elongation at break>=50%; Volume specific resistance>=1.0 × 10
9Ω .cm, <1.0 × 10
13Ω .cm; Specific inductivity>=15; Dielectric loss value≤0.8;
At present, in existing thermal contraction cable accessory middle high-pressure voltage grades such as (mainly) 6kV, 10kV, 20kV and 35kV, the material of thermal contraction electric stress control tube is all with CPE(chlorinatedpolyethylene) be material of main part, because the material behavior of CPE determines the general technical requirement that its performance such as heat-proof aging, radiation hardness cannot meet used in nuclear power station 1E level K1 class middle high-pressure thermal contraction cable accessory.
Summary of the invention
The technical problem to be solved in the present invention is: in order to overcome the defect that existing used in nuclear power station 1E level K1 class thermal contraction electric stress control tube exists, there is provided a kind of used in nuclear power station 1E level K1 class thermal contraction electric stress control tube and preparation method thereof, its heat-proof aging, radiation hardness, specific inductivity are high, dielectric loss value is low, volume specific resistance is evenly distributed.
In order to solve the problems of the technologies described above, the present invention proposes following technical scheme: a kind of used in nuclear power station 1E level K1 class thermal contraction electric stress control tube, is made up of the following component according to weight parts:
Crystallinity terpolymer EP rubber 70-100 part;
Polyethylene 0-30 part;
Modified barium carbonate 10-30 part;
High wear-resistant carbon black 20-40 part;
Sensitizing agent 2-5 part;
Anti-aging agent 2-4 part;
Anti-irradiation agent 5-10 part;
Lubricant 2-4 part;
The degree of crystallinity of described crystallinity terpolymer EP rubber is 10-28%, and mooney viscosity scope is 22-60, and ethylene content is 50-70Wt%, ENB content is 0.5-5%;
Described poly relative density is 0.92-0.96, and degree of crystallinity is 40%-80%, and fusing point is 103-130 DEG C, and melting index is 0.1-3.0g/10min;
The particle size range of described modified barium carbonate is 1.0-10 μm;
Described high wear-resistant carbon black particle diameter is 20-30nm;
Described sensitizing agent is one or more the mixture in following substances: cyanacrylate, trimethylolpropane trimethacrylate, Viscoat 295;
Described anti-aging agent is one or more the mixture in following substances: N-phenyl-a-naphthylamine; N-Phenyl beta naphthylamine; N, N'-bis-(betanaphthyl) Ursol D;
Described anti-irradiation agent is one or more the mixture in following substances: silicon nitride, norbide;
The particle size range of described anti-irradiation agent is 1.0-10 μm;
Described lubricant is one or more the mixture in following substances: polyethylene wax, stearic acid, Zinic stearas, Magnesium Stearate or calcium stearate.
In order to solve the problems of the technologies described above, the present invention proposes following technical scheme: a kind of preparation method of used in nuclear power station 1E level K1 class thermal contraction electric stress control tube: get crystallinity terpolymer EP rubber 70-100 part, polyethylene 0-30 part, modified barium carbonate 10-30 part, high wear-resistant carbon black 20-40 part, sensitizing agent 2-5 part, anti-aging agent 2-4 part, anti-irradiation agent 5-10 part, lubricant 2-4 part, said components through mixer mixing granulation, then homogenize in 25-30 minute is stirred through stirrer, again through parallel double-screw extruder mixing granulator, then tubing is extruded into single screw extrusion machine, described tubing is through Co 60 or rumbatron 80 ~ 180KGy radiation crosslinking, tubing after radiation crosslinking expands 2 ~ 4 times at 120 ~ 180 DEG C of temperature.
Compared with prior art, the present invention has following beneficial effect:
1. carbon black, barium titanate are added in crystallinity terpolymer EP rubber, by optimizing respective adding proportion, except the mechanical property requirements of heat-shrinkage material routine can be reached: tensile strength>=9Mpa; Elongation at break>=250%; The electric property of expection can also be reached: volume specific resistance>=1.0 × 10
9Ω .cm, <1.00 × 10
13Ω .cm; Specific inductivity>=25; Dielectric loss≤0.8; And then obtain the function of the control electric field stress required for thermal contraction cable accessory.
2. the amines antioxidants of high comprehensive performance, carbon black and boron nitride anti-irradiation agent share, can give with crystallization star ethylene propylene diene monomer (EPDM) material outstanding high temperature resistant, radiation-resistant performance, meet Nuclear power plants to the requirement using 60 years at used in nuclear power station 1E level K1 class heat-shrinkable tube 90 DEG C of temperature, be embodied in: 175 DEG C, 230 h heat aging time, after radiation dose 2400KGy: tensile strength>=5.5MPa; Elongation at break>=50%; Volume specific resistance>=1.0 × 10
9Ω .cm, <1.00 × 10
13Ω .cm; Specific inductivity>=15; Dielectric loss≤0.8.
3. used in nuclear power station 1E level K1 class thermal contraction electric stress control tube of the present invention, not containing halogen, can meet the test request of used in nuclear power station 1E level K1 class cable and annex halogen acid gas thereof.
Embodiment
The present invention proposes a kind of used in nuclear power station 1E level K1 class thermal contraction electric stress control tube, is made up of the following component according to weight parts:
Crystallinity terpolymer EP rubber 70-100 part;
Polyethylene 0-30 part;
Modified barium carbonate 10-30 part;
High wear-resistant carbon black 20-40 part;
Sensitizing agent 2-5 part;
Anti-aging agent 2-4 part;
Anti-irradiation agent 5-10 part;
Lubricant 2-4 part.
The degree of crystallinity of described crystallinity terpolymer EP rubber is 10-28%, and mooney viscosity scope is 22-60, and ethylene content is 50-70Wt%, ENB content is 0.5-5%.
Described poly relative density is 0.92-0.96, and degree of crystallinity is 40%-80%, and fusing point is 103-130 DEG C, and melting index is 0.1-3.0g/10min.
The particle size range of described modified barium carbonate is 1.0-10 μm.
Described high wear-resistant carbon black is that Audit For Process is produced, and particle diameter is 20-30nm.
Described sensitizing agent is the one in following substances: cyanacrylate (TAIC), trimethylolpropane trimethacrylate (TMPTMA) or (Viscoat 295 TMPTA).
Described anti-aging agent is one or more the mixture in following substances: N-phenyl-a-naphthylamine; N-Phenyl beta naphthylamine; N, N'-bis-(betanaphthyl) Ursol D;
Described anti-irradiation agent is one or more the mixture in following substances: silicon nitride, norbide.
The particle size range of described anti-irradiation agent is 1.0-10 μm.
Described lubricant is one or more the mixture in following substances: polyethylene wax, stearic acid, Zinic stearas, Magnesium Stearate or calcium stearate.
The preparation method of above-mentioned used in nuclear power station 1E level K1 class thermal contraction electric stress control tube is as follows: get crystallinity terpolymer EP rubber 70-100 part, polyethylene 0-30 part, modified barium carbonate 10-30 part, high wear-resistant carbon black 20-40 part, sensitizing agent 2-5 part, anti-aging agent 2-4 part, anti-irradiation agent 5-10 part, lubricant 2-4 part.Said components through mixer mixing granulation, then homogenize in 25-30 minute is stirred through stirrer, again through parallel double-screw extruder mixing granulator, then tubing is extruded into single screw extrusion machine, described tubing is through Co 60 or rumbatron 80 ~ 180KGy radiation crosslinking, and the tubing after radiation crosslinking expands 2 ~ 4 times at 120 ~ 180 DEG C of temperature.
preparation embodiment and comparative example thereof
preparation embodiment 1
Take crystallinity terpolymer EP rubber (DOW chemical company NORDEL IP4820P) 100 parts, polyethylene 0 part, modified barium carbonate (Shanghai allusion quotation raises company's T 304) 30 parts, high wear-resistant carbon black (Cabot N330) 20 parts, sensitizing agent TAIC(Shanghai Fang Ruida by weight) 3 parts, anti-aging agent N-phenyl-a-naphthylamine (state's marine life) 2 parts, anti-irradiation agent silicon nitride (institute is ground in Dandong) 5 parts, lubricant stearic acid (commercially available) 4 parts.
Above-mentioned materials is through mixer mixing granulation, 30 minutes are stirred with stirrer, then through parallel double-screw extruder mixing granulator, tubing is extruded into single screw extrusion machine, described tubing is through Co 60 or rumbatron 80KGy radiation crosslinking, tubing after radiation crosslinking expands 4 times at 120 DEG C of temperature, obtains thermal contraction electric stress control tube.
preparation embodiment 2
Take crystallinity terpolymer EP rubber (DOW chemical company NORDEL IP4760P) 70 parts by weight, polyethylene (Yanshan Petrochemical LDPE1I2A) 30 parts, modified barium carbonate (Shanghai allusion quotation raises company's T 304) 10 parts, high wear-resistant carbon black 40 parts (being made up of Cabot N55015 part and Cabot N22025 part), sensitizing agent TMPTMA(U.S. Sartomer SR350) 2 parts, 4 parts, anti-aging agent is (by N-phenyl-a-naphthylamine (state's marine life) 2 parts, N-Phenyl beta naphthylamine (state's marine life) 2 parts composition), anti-irradiation agent norbide (Mudanjiang advance) 10 parts, 2 parts, lubricant stearic acid zinc (commercially available).
Above-mentioned materials is through mixer mixing granulation, 30 minutes are stirred with stirrer, then through parallel double-screw extruder mixing granulator, tubing is extruded into single screw extrusion machine, described tubing is through Co 60 or rumbatron 180KGy radiation crosslinking, tubing after radiation crosslinking expands 2.5 times at 180 DEG C of temperature, obtains thermal contraction electric stress control tube.
preparation embodiment 3
Take crystallinity terpolymer EP rubber (DOW chemical company NORDEL IP3745P) 85 parts, polyethylene (Borealis MDPE2310) 15 parts, modified barium carbonate (Shanghai Dian Yang company) 20 parts, high wear-resistant carbon black (Cabot N550) 25 parts, sensitizing agent TMPTA(U.S. Sartomer SR351 by weight) 5 parts, anti-aging agent N-phenyl-a-naphthylamine (state's marine life) 4 parts, anti-irradiation agent silicon nitride (institute is ground in Dandong) 5 parts, lubricant stearic acid calcium (commercially available) 3 parts.
Above-mentioned materials is through mixer mixing granulation, 30 minutes are stirred with stirrer, then through parallel double-screw extruder mixing granulator, tubing is extruded into single screw extrusion machine, described tubing is through Co 60 or rumbatron 140KGy radiation crosslinking, tubing after radiation crosslinking expands 2 times at 150 DEG C of temperature, obtains thermal contraction electric stress control tube.
comparative example
Take polyethylene (Yanshan Petrochemical LDPE1I2A) by weight: 35 parts; The organic 14-2 in EVA(north): 20 parts; CPE(AsiaSat 135A): 45 parts; Modified barium carbonate (Shanghai allusion quotation raises company's T 304): 45 parts; High wear-resistant carbon black (Cabot N330): 20 parts; N-phenyl-a-naphthylamine (state's marine life): 2 parts; N-Phenyl beta naphthylamine (state's marine life): 2 parts; Thermo-stabilizer (Hongyuan chemical industry G301): 4 parts.
Above-mentioned materials is through mixer mixing granulation, 30 minutes are stirred with stirrer, then through parallel double-screw extruder mixing granulator, tubing is extruded into single screw extrusion machine, described tubing is through Co 60 or rumbatron 100KGy radiation crosslinking, tubing after radiation crosslinking expands 2.5 times at 150 DEG C of temperature, obtains thermal contraction electric stress control tube.
The experimental test result of above-described embodiment and comparative example is as shown in table 1.
Table 1
Comparing embodiment 1 to embodiment 3 finds with the test result of comparative example, and the thermal contraction electric stress control tube described in comparative example (containing CPE composition) cannot pass through the thermal ageing test of 175 DEG C, 230 hours and follow-up test thereof.And the present invention apply for that the thermal contraction electric stress control tube (embodiment 1,2 and 3) protected all can meet the performance test of thermal contraction electric stress control tube in used in nuclear power station 1E level K1 class thermal contraction cable accessory.
Claims (2)
1. a used in nuclear power station 1E level K1 class thermal contraction electric stress control tube, is characterized in that, it is made up of the following component according to weight parts:
Crystallinity terpolymer EP rubber 70-100 part;
Polyethylene 0-30 part;
Modified barium carbonate 10-30 part;
High wear-resistant carbon black 20-40 part;
Sensitizing agent 2-5 part;
Anti-aging agent 2-4 part;
Anti-irradiation agent 5-10 part;
Lubricant 2-4 part;
The degree of crystallinity of described crystallinity terpolymer EP rubber is 10-28%, and mooney viscosity scope is 22-60, and ethylene content is 50-70Wt%, ENB content is 0.5-5%;
Described poly relative density is 0.92-0.96, and degree of crystallinity is 40%-80%, and fusing point is 103-130 DEG C, and melting index is 0.1-3.0g/10min;
The particle size range of described modified barium carbonate is 1.0-10 μm;
Described high wear-resistant carbon black particle diameter is 20-30nm;
Described sensitizing agent is one or more the mixture in following substances: cyanacrylate, trimethylolpropane trimethacrylate, Viscoat 295;
Described anti-aging agent is one or more the mixture in following substances: N-phenyl-a-naphthylamine; N-Phenyl beta naphthylamine; N, N'-bis-(betanaphthyl) Ursol D;
Described anti-irradiation agent is one or more the mixture in following substances: silicon nitride, norbide;
The particle size range of described anti-irradiation agent is 1.0-10 μm;
Described lubricant is one or more the mixture in following substances: polyethylene wax, stearic acid, Zinic stearas, Magnesium Stearate or calcium stearate.
2. the preparation method of a used in nuclear power station 1E level K1 class thermal contraction electric stress control tube as claimed in claim 1, it is characterized in that: get crystallinity terpolymer EP rubber 70-100 part, polyethylene 0-30 part, modified barium carbonate 10-30 part, high wear-resistant carbon black 20-40 part, sensitizing agent 2-5 part, anti-aging agent 2-4 part, anti-irradiation agent 5-10 part, lubricant 2-4 part, said components through mixer mixing granulation, then homogenize in 25-30 minute is stirred through stirrer, again through parallel double-screw extruder mixing granulator, then tubing is extruded into single screw extrusion machine, described tubing is through Co 60 or rumbatron 80 ~ 180KGy radiation crosslinking, tubing after radiation crosslinking expands 2 ~ 4 times at 120 ~ 180 DEG C of temperature.
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| CN111849082A (en) * | 2020-08-07 | 2020-10-30 | 无锡市中汇线缆股份有限公司 | Cable core wire insulating material with water resistance |
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| CN105462083B (en) | 2017-11-10 |
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