CN103910968B - Cable insulating material of resistance to nuclear environment and preparation method thereof - Google Patents
Cable insulating material of resistance to nuclear environment and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of cable insulating material of resistance to nuclear environment, its quality component：For EPM methylmethacrylate copolymer：100 parts；The mixture of nano-aluminum hydroxide and aluminium hydroxide：135~145 parts；Calcined kaolin：15~20 parts；The mixture of the dihyaroquinoline of 2,2,4 trimethyl 1,2 and N isopropyl N' diphenyl-para-phenylene diamines：2.5~4.5 parts；The mixture of double (piperidyl of 2,2,6,6 tetramethyl 4) 1,3 benzenedicarboxamides of N, N' and 2 (2' hydroxyl 5' t-octyls phenyl) BTAs：2.5~3.6 parts etc..The preparation method of this Insulation Material is：By dispensing successively by mixing, filter rubber, mixing, bottom sheet, extrusion operation, it is made under special process parameter request.This product solves the technical barrier such as radiation-resistant property difference under the high radiation parameter of wireline environment, meets the demand of this special high request occasion of generation Ⅲ nuclear power station, the requirement for the cable insulating material of resistance to nuclear environment is fully achieved.
Description
Technical field
The invention belongs to field of cable technology, and in particular to a kind of cable insulating material, more particularly relate to a kind of resistance to nuclear ring
Border cable insulating material and preparation method thereof, suitable for having the generation Ⅲ nuclear power station of particular/special requirement to cable insulating material especially
The use of AP1000 shell inner cables.
Background technology
Increasingly harsh Energy situation brings huge development space to Chinese Nuclear Power construction, represents nuclear power advanced technology
Generation Ⅲ nuclear power station every auxiliary products are proposed with very harsh requirement, converged the elite of all trades and professions technology, according to
The requirement for the cable insulating material that generation Ⅲ nuclear power station proposes, cable insulating material will have extraordinary resistance to long term heat ageing performance,
Can normal operation more than 60 years, there is the gamma-rays of resistance to high dose and Beta-ray irradiation behaviour, and require that cable insulating material possesses
Chemically-resistant spray, high temperature resistant, fire-retardant, electrical insulation properties, the performance such as low-smoke zero-halogen low-toxicity performance.
In nuclear power station operation, cable insulating material needs to bear the environment such as heat, oxygen, irradiation, high under long term thermal, oxygen aging
Crosslinking and degradation reaction occurs in molecular material, and strand constantly forms the fracture of branched structure and molecular link, with environment
The invasion of oxygen and ozone, trigger polymer c h bond to produce chain type radical reaction, make c h bond fracture generation free radical, generation
Free radical can further capture hydrogen atom most active on polymer so that radical reaction is carried out continuously, and constantly causes material
The degraded of material.In addition, Polymer Materials ' Structure division and isomerization can also be caused in the presence of heat and oxygen, and generate aldehyde and alcohol
Formation, be further exacerbated by the reaction of free radical, while also can be along with the fracture of main chain C-C keys in molecule.
Insulating materials is chronically exposed to the rays such as the gamma-rays of high-energy, β rays under irradiation, and high polymer material can be sent out
The fracture of sub-key estranged and cross-linking reaction, so that the molecular weight of material and structure change, high-energy ray is passed by energy
Pass, polymer molecule is produced ionization, accelerate the aging of material.Some cable materials can produce substantial amounts of smog in fire
And hydrogen halide, personnel and equipment are caused with very big destruction, therefore cable insulating material has low cigarette, Halogen, low toxicity
Performance is necessary.Steam line break caused by nuclear power plant accident operating mode, HTHP impact is to electricity caused by moment
Cable material has very strong destruction, and chemical spray is to corrosiveness caused by cable material meeting at high temperature, and influences exhausted
The electric property and ageing properties of edge material.To reach fire-retardant purpose, cable insulation material requires to add substantial amounts of fire retardant, but
Such a way causes the mechanical performance of insulating materials, electrical insulation properties to be greatly affected；Therefore it is satisfaction insulation
Material is heat-resisting, resistance to irradiation, fire-retardant and electric property, current cable insulating material is unapproachable, particularly require 60 years with
On service life be even more difficult test to existing cable Insulation Material, but at present generation Ⅲ nuclear power station foundation, especially
The popularization and application of AP1000 nuclear power technologies, but this problem in the urgent need to address, it is necessary to performance is good, service life up to 60 years with
On cable insulating material.
The content of the invention
In order to solve the above-mentioned problems in the prior art, the invention provides a kind of performance is good, service life is up to 60
Used more than year, suitable for generation Ⅲ nuclear power station, especially with the cable insulating material of resistance to nuclear environment in AP1000 nuclear power stations shell.This hair
Bright concrete technical scheme is as follows：
A kind of cable insulating material of resistance to nuclear environment, include following component according to mass fraction meter：
EPM-methylmethacrylate copolymer：100 parts；
The mixture of nano-aluminum hydroxide and aluminium hydroxide：135~145 parts；
Calcined kaolin：15~20 parts；
2,2,4- trimethyl -1,2- dihyaroquinolines（Condensate）With the mixing of N- isopropyl-N'- phenyl-pphenylenediamines
Thing：2.5~4.5 parts；
Double (2,2,6,6- tetramethyl -4- the piperidyls) -1,3- benzenedicarboxamides of N, N'- and 2- (2'- hydroxyl -5'- t-octyls
Phenyl) BTA mixture：2.5~3.6 parts；
Nano zine oxide：4~6 parts；
The mixture of paraffin and microwax：6~9 parts；
Vinyl three ('beta '-methoxy ethyoxyl) silane：2.5~3.5 parts；
The double tert-butyl peroxide hexanes of 2,5- dimethyl -2,5-：3~3.5 parts；
Triallyl isocyanurate：1.2~1.6 parts.
In the EPM-methylmethacrylate copolymer, EPM and methyl methacrylate
Mass percent be 91: 9；
The nano-aluminum hydroxide and aluminium hydroxide are (10~13) according to mass ratio: (125~132) mixing, nanometer hydrogen
The average grain diameter of aluminum oxide is 20nm, and specific surface area is 200-300 m2/ g, 1.0~1.5 μm of aluminium hydroxide average grain diameter；
2,2,4- trimethyls -1,2- dihyaroquinolines and the N- isopropyl-N'- phenyl-pphenylenediamines are according to mass ratio
Mixed for (1.0~1.5): (1.5~3)；
Double (2,2,6,6- tetramethyl -4- the piperidyls) -1,3- benzenedicarboxamides of the N, N'- and 2- (2'- hydroxyl -5'- uncles
Octyl phenyl) BTA according to mass ratio is (1.5~2): (1~1.6) mixing.
The average grain diameter of the nano zine oxide is 30nm.
The paraffin and microwax are (2.5~4) according to mass ratio: (3.5~5) mix.
Vinyl three ('beta '-methoxy ethyoxyl) silane.
The double tert-butyl peroxide hexanes of the 2,5- dimethyl -2,5-.
The Triallyl isocyanurate.
Above-mentioned EPM-methylmethacrylate copolymer has good to the inorganic filler in other preparations
Compatibility, due to there is no double bond in the plastic structure of binary second third, aging of the base-material under air ambient is effectively slow down, with methyl-prop
After e pioic acid methyl ester copolymer, extraordinary heat-resisting, resistance to ozone, water absorption resistance, high temperature resistant, low temperature resistant, acid and alkali-resistance, resistance toization are shown
Medicine and anti-radiation performance are learned, and there are good electrical insulation properties.
It is used cooperatively using nano-aluminum hydroxide and aluminium hydroxide, material combustion effect can be eliminated smoke and reduce, from receiving
Rice aluminium hydroxide average grain diameter 20nm, specific surface area 200-300 m2/ g, there is larger specific surface area, nano-aluminum hydroxide table
Face activity is high, by playing rigid plasticization, improves the mechanical property of material, and can improve any surface finish of insulation
Degree, electrical insulation properties and anti-electric creepage performance.Nano-aluminum hydroxide has higher structural, the formation densification after material combustion
Structure sheaf, it is effective to suppress melting drippage during polymer combustion.
The calcined kaolin has good plasticity and has excellent electrical insulation capability, and use is cooperateed with aluminium hydroxide
When, it can generate stable layer of charcoal support frame by uniformly disperseing, during burning, deformation of the resistance material under combustion high temperature,
The ceramic structure that burning is formed is advantageous to improve the refractory temperature of material, while also contributes to improve the exhausted of ethyl-propylene insulating materials
Edge resistance and breakdown strength.
2,2,4- trimethyl -1,2- dihyaroquinolines have pole to aging caused by hot, oxygen during second the third glue long-term use
Good protective action, and there is long-acting heat resistance, with N- isopropyl-N'- phenyl-pphenylenediamines, N, N'- double (2,2,6,6-
Tetramethyl -4- piperidyls) -1,3- benzenedicarboxamides, 2- (2'- hydroxyl -5'- t-octyls phenyl) BTA, nanometer hydroxide
Aluminium, nano zine oxide are used cooperatively, and make the molecular structure that special phenyl ring is introduced in polymer molecular structure, and being changed by interior energy will
Radiation energy is converted into heat energy, improves heat-resistant stability and radiation resistance under insulating materials long-term use environment.Nuclear power station
A large amount of ozone have very big destruction to high polymer material caused by containment kernel reactor operation, it is desirable to cable
Material possesses excellent ozone resistance, by the selection of above preparation, coordinates N, double (2,2,6, the 6- tetramethyl -4- piperidines of N'-
Base) -1,3- benzenedicarboxamides, the cooperative effect of 2- (2'- hydroxyl -5'- t-octyls phenyl) BTA, effectively increase insulation
Heat-resisting, resistance to ozone and radiation resistance of the material under operating condition.
A kind of preparation method for the cable insulating material of resistance to nuclear environment, step include：
1）The raw material of cable insulating material is subjected to weighing and burden according to formula；
2）Then by the mixing of EPM methylmethacrylate copolymer, nano-aluminum hydroxide and aluminium hydroxide
Thing and vinyl three ('beta '-methoxy ethyoxyl) silane in dispersion machine with（500±50）Rev/min mixing speed stir
Mix；
During stirring, first dispersion machine is carried out to be preheating to 70-75 DEG C, then nano-aluminum hydroxide and the mixture of aluminium hydroxide
Feed intake stirring 4~6 minutes；Vinyl three ('beta '-methoxy ethyoxyl) silane is subsequently added into, is stirred for 5~7 minutes；It is eventually adding
EPM methylmethacrylate copolymer, it is stirred for discharging after 4~6 minutes；
3）Step 2）Obtained product and paraffin and mixture, the N of microwax, the double (2,2,6,6- tetramethyls -4- of N'-
Piperidyl) mixture of -1,3- benzenedicarboxamides and 2- (2'- hydroxyl -5'- t-octyls phenyl) BTA, nano zine oxide,
Calcined kaolin and 2,2,4- trimethyl -1,2- dihyaroquinolines and the mixing of N- isopropyl-N'- phenyl-pphenylenediamines
Thing carries out mixing 10~12 minutes, the discharging when temperature is 135 DEG C；
4）By step 3）Obtained product adds the double tert-butyl peroxide hexanes of 2,5- dimethyl -2,5- and triallyl isocyanide
It is kneaded after urea acid esters, sheet stock is finally made；
5）Finally by step 4）Obtained sheet stock, which carries out extrusion, to be processed and produces the cable insulating material of resistance to nuclear environment.
Step 4）In, step 3）Obtained product first carries out filter rubber, then carries out subsequent job.
Cable insulating material fire resistance provided by the invention is good, and electrical insulation properties are good, and it is gamma-ray to can be resistant to high dose
Irradiation, resistance to long term heat ageing performance is good, and water absorption resistance can be strong and meets low smoke, zero halogen low toxicity performance.The present invention is to cable insulating material
Innovation, solve that current cable insulating material service life is short, the technology such as radiation-resistant property difference under the high radiation parameter of wireline environment
Problem, the demand of this special high request occasion of generation Ⅲ nuclear power station is met, the cable insulating material of resistance to nuclear environment is fully achieved
Requirement.
Embodiment
With reference to embodiment, the present invention is further detailed explanation.
The preparation method of the cable insulating material of resistance to nuclear environment of this example, step are as follows：
1）The raw material of cable insulating material is subjected to weighing and burden according to formula；
2）Then by the mixing of EPM methylmethacrylate copolymer, nano-aluminum hydroxide and aluminium hydroxide
Thing and vinyl three ('beta '-methoxy ethyoxyl) silane in dispersion machine with（500±50）Rev/min mixing speed stir
Mix；
During stirring, first dispersion machine is carried out to be preheating to 70~75 DEG C, then the mixing nano-aluminum hydroxide and aluminium hydroxide
Thing feeds intake stirring 4~6 minutes；Vinyl three ('beta '-methoxy ethyoxyl) silane is subsequently added into, is stirred for 5~7 minutes；Finally plus
Enter EPM methylmethacrylate copolymer, be stirred for discharging after 4~6 minutes；
3）Step 2）Obtained product and paraffin and mixture, the N in banbury of microwax, the double (2,2,6,6- of N'-
Tetramethyl -4- piperidyls) -1,3- benzenedicarboxamides and 2- (2'- hydroxyl -5'- t-octyls phenyl) BTA mixture, receive
Rice zinc oxide, calcined kaolin and 2,2,4- trimethyl -1,2- dihyaroquinolines and N- isopropyl-N'- phenyl-to benzene two
The mixture of amine carries out mixing 10~12 minutes, the discharging when temperature is 135 DEG C；
4）By step 3）Obtained product first carries out filter rubber in filter rubber machine；Then 2,5- dimethyl -2 are added in banbury,
It is kneaded after the double tert-butyl peroxide hexanes of 5- and Triallyl isocyanurate, most obtains sheet stock through grinding page mechanism afterwards；
5）Finally by step 4）Obtained sheet stock extrudes stranding through rubber extruding machine, obtains the cable insulating material of resistance to nuclear environment.
Height employed in this preparation process stirs machine（Homogenizer is dispersion machine）, banbury, filter rubber machine, three rollers grind page
Machine, rubber extruding machine equipment use existing equipment.
In embodiment：EPM in EPM-methylmethacrylate copolymer accounts for gross mass
91%；The average grain diameter of nano-aluminum hydroxide is 20nm, and specific surface area is 200-300 m2/g；Aluminium hydroxide average grain diameter is 1.0
~1.5 μm；The average grain diameter of zinc oxide is 30nm.
Embodiment 1
A kind of cable insulating material of resistance to nuclear environment, it is made up of following material according to mass fraction：
100 parts of EPM methylmethacrylate copolymer；
10 parts of nano-aluminum hydroxide；
125 parts of aluminium hydroxide；
15 parts of calcined kaolin；
1.0 parts of 2,2,4- trimethyl -1,2- dihyaroquinolines；
2.8 parts of N- isopropyl-N'- phenyl-pphenylenediamines；
Double (2,2,6,6- tetramethyl -4- piperidyls) the 1.5 parts of -1,3- benzenedicarboxamides of N, N'-；
2- (2'- hydroxyl -5'- t-octyls phenyl) 1 part of BTA；
4.0 parts of zinc oxide；
2.5 parts of paraffin；
3.5 parts of microwax；
2.5 parts of vinyl three ('beta '-methoxy ethyoxyl) silane；
Double 3.0 parts of the tert-butyl peroxide hexanes of 2,5- dimethyl -2,5-；
1.2 parts of Triallyl isocyanurate.
The preparation method of the above-mentioned cable insulating material of resistance to nuclear environment, step are as follows：
By EPM-methylmethacrylate copolymer, nano-aluminum hydroxide, aluminium hydroxide, vinyl three (β-
Methoxy ethoxy) silane in 70-75 DEG C, stirred in machine in height, in 500 revs/min of agitator speeds pre-dispersed 7-11 minutes,
It is double with paraffin, microwax, 2,2,4- trimethyl -1,2- dihyaroquinolines, N- isopropyl-N'- phenyl-pphenylenediamines, N, N'- again
(2,2,6,6- tetramethyl -4- piperidyls) -1,3- benzenedicarboxamides, 2- (2'- hydroxyl -5'- t-octyls phenyl) BTA, oxygen
Change zinc, calcined kaolin is sent into banbury and is kneaded 11 minutes together；Mixed material is sent into filter rubber machine and carries out filter rubber,
Then it is sent into banbury after being kneaded with -2,5- pairs of tert-butyl peroxide hexanes of 2,5- dimethyl and Triallyl isocyanurate
Carry out three rollers and grind page machine bottom sheet, obtain sheet stock, above-mentioned sheet stock is finally sent into rubber extruding machine extrusion stranding, obtains the cable of resistance to nuclear environment
Insulation Material, its performance data are shown in Table 1.
Embodiment 2
A kind of cable insulating material of resistance to nuclear environment, it is made up of following material according to mass fraction：
100 parts of EPM methylmethacrylate copolymer；
13 parts of nano-aluminum hydroxide；
132 parts of aluminium hydroxide；
20 parts of calcined kaolin；
1.5 parts of 2,2,4- trimethyl -1,2- dihyaroquinolines；
3.0 parts of N- isopropyl-N'- phenyl-pphenylenediamines；
Double (2,2,6,6- tetramethyl -4- piperidyls) the 2.0 parts of -1,3- benzenedicarboxamides of N, N'-；
2- (2'- hydroxyl -5'- t-octyls phenyl) 1.6 parts of BTA；
6.0 parts of zinc oxide；
4.0 parts of paraffin；
5.0 parts of microwax；
3.5 parts of vinyl three ('beta '-methoxy ethyoxyl) silane；
Double 3.5 parts of the tert-butyl peroxide hexanes of 2,5- dimethyl -2,5-；
1.6 parts of Triallyl isocyanurate.
The preparation method for the cable insulating material of resistance to nuclear environment is same as Example 1 in the present embodiment, and its performance data is shown in Table 1.
Embodiment 3
A kind of cable insulating material of resistance to nuclear environment, it is made up of following material according to mass fraction：
100 parts of EPM methylmethacrylate copolymer；
12 parts of nano-aluminum hydroxide；
128 parts of aluminium hydroxide；
19 parts of calcined kaolin；
1.2 parts of 2,2,4- trimethyl -1,2- dihyaroquinolines；
2.6 parts of N- isopropyl-N'- phenyl-pphenylenediamines；
Double (2,2,6,6- tetramethyl -4- piperidyls) the 1.6 parts of -1,3- benzenedicarboxamides of N, N'-；
2- (2'- hydroxyl -5'- t-octyls phenyl) 1.3 parts of BTA；
5.0 parts of zinc oxide；
3.0 parts of paraffin；
4.0 parts of microwax；
3.0 parts of vinyl three ('beta '-methoxy ethyoxyl) silane；
Double 3.2 parts of the tert-butyl peroxide hexanes of 2,5- dimethyl -2,5-；
1.4 parts of Triallyl isocyanurate.
The preparation method for the cable insulating material of resistance to nuclear environment is same as Example 1 in the present embodiment, and its performance data is shown in Table 1.
Comparative example 1
A kind of cable insulating material of resistance to nuclear environment, it is made up of following material according to mass fraction：
100 parts of EPM methylmethacrylate copolymer；
15 parts of magnesium hydroxide；
135 parts of aluminium hydroxide；
1.3 parts of 2,2,4- trimethyl -1,2- dihyaroquinolines；
2.5 parts of N- isopropyl-N'- phenyl-pphenylenediamines；
Double (2,2,6,6- tetramethyl -4- piperidyls) the 1.6 parts of -1,3- benzenedicarboxamides of N, N'-；
2- (2'- hydroxyl -5'- t-octyls phenyl) 1.3 parts of BTA；
5.0 parts of common zinc oxide；
3.0 parts of paraffin；
4.0 parts of microwax；
2.5 parts of vinyl three ('beta '-methoxy ethyoxyl) silane；
Double 3.2 parts of the tert-butyl peroxide hexanes of 2,5- dimethyl -2,5-；
1.3 parts of Triallyl isocyanurate.
The preparation method for the cable insulating material of resistance to nuclear environment is same as Example 1 in the present embodiment, and formula does not use nanometer hydrogen
The components such as aluminum oxide, calcined kaolin, nano zine oxide, its performance data are shown in Table 1, insulating materials life-span, LOCA examinations in the example
Test and fail to occur declining in various degree up to regulation requirement, mechanical performance, insulation water absorption test with single combustion test, therefore this
The combination of materials that patent uses is to solving the performances such as high dose radiation hardness, fire-retardant, long term heat ageing experiment, high temperature resistant, water absorption resistance
With significant effect.
Table 1
Claims (3)
1. a kind of cable insulating material of resistance to nuclear environment, it is characterised in that include following component according to mass fraction meter：
EPM-methylmethacrylate copolymer：100 parts, wherein, EPM and methyl methacrylate
Mass percent be 91: 9；
The mixture of nano-aluminum hydroxide and aluminium hydroxide：135~145 parts, wherein, the average grain diameter of nano-aluminum hydroxide is
20nm, specific surface area 200-300m2/g；Aluminium hydroxide average grain diameter is 1.0~1.5 μm；The nano zine oxide, average grain
Footpath 30nm；
Calcined kaolin：15~20 parts；
2,2,4- trimethyl -1,2- dihyaroquinolines and the mixture of N- isopropyl-N'- phenyl-pphenylenediamines：2.5~4.5
Part, wherein, 2,2,4- trimethyl -1,2- dihyaroquinolines and N- isopropyl-N'- phenyl-pphenylenediamines are according to mass ratio
(1.0~1.5): (1.5~3) mixing；
Double (2,2,6,6- tetramethyl -4- the piperidyls) -1,3- benzenedicarboxamides of N, N'- and 2- (2'- hydroxyl -5'- t-octyl benzene
Base) BTA mixture：2.5~3.6 parts, wherein, double (2,2,6,6- tetramethyl -4- piperidyls) -1, the 3- benzene two of N, N'-
Formamide and 2- (2'- hydroxyl -5'- t-octyls phenyl) BTA are (1.5~2) according to mass ratio: (1~1.6) mixing；
Nano zine oxide：4~6 parts；
The mixture of paraffin and microwax：6~9 parts, wherein, paraffin and microwax are (2.5~4) according to mass ratio: (3.5~
5) mix；
Vinyl three ('beta '-methoxy ethyoxyl) silane：2.5~3.5 parts；
The double tert-butyl peroxide hexanes of 2,5- dimethyl -2,5-：3~3.5 parts；
Triallyl isocyanurate：1.2~1.6 parts.
2. the preparation method of the cable insulating material of resistance to nuclear environment described in a kind of claim 1, it is characterised in that step includes：
1) raw material of cable insulating material is subjected to weighing and burden according to formula；
2) then by the mixture of EPM-methylmethacrylate copolymer, nano-aluminum hydroxide and aluminium hydroxide,
And vinyl three ('beta '-methoxy ethyoxyl) silane is stirred in dispersion machine with 500 revs/min ± 50 revs/min of mixing speed
Mix；
During stirring, first dispersion machine is carried out to be preheating to 70~75 DEG C, then throw the mixture of nano-aluminum hydroxide and aluminium hydroxide
Material stirring 4~6 minutes；Vinyl three ('beta '-methoxy ethyoxyl) silane is subsequently added into, is stirred for 5~7 minutes；It is eventually adding two
First EP rubbers methylmethacrylate copolymer, is stirred for discharging after 4~6 minutes；
3) product that step 2) is obtained and paraffin and mixture, the N of microwax, the double (2,2,6,6- tetramethyl -4- piperidines of N'-
Base) mixture of -1,3- benzenedicarboxamides and 2- (2'- hydroxyl -5'- t-octyls phenyl) BTA, nano zine oxide, calcining
Kaolin and 2,2,4- trimethyl -1,2- dihyaroquinolines and the mixture of N- isopropyl-N'- phenyl-pphenylenediamines are carried out
It is kneaded 10~12 minutes, the discharging when temperature is 135 DEG C；
4) product for obtaining step 3) adds the double tert-butyl peroxide hexanes of 2,5- dimethyl -2,5- and triallyl isocyanuric acid
It is kneaded after ester, sheet stock is finally made；
5) sheet stock made from step 4) finally carried out into extrusion processed to produce the cable insulating material of resistance to nuclear environment.
3. preparation method according to claim 2, it is characterised in that in step 4), the product that step 3) is obtained first is carried out
Rubber is filtered, then carries out subsequent job.
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| CN111534198A (en) * | 2020-04-22 | 2020-08-14 | 上海闰龙电子材料有限公司 | Formula and preparation method of single-component insulation protection material for thermistor |
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| CN102120863A (en) * | 2011-01-17 | 2011-07-13 | 江苏上上电缆集团有限公司 | Cable insulant for third-generation nuclear power station and preparation method thereof |
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