CN103524963B - Formula of semiconductive internal shielding material for scorch preventing cable - Google Patents
Formula of semiconductive internal shielding material for scorch preventing cable Download PDFInfo
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- CN103524963B CN103524963B CN201310508136.9A CN201310508136A CN103524963B CN 103524963 B CN103524963 B CN 103524963B CN 201310508136 A CN201310508136 A CN 201310508136A CN 103524963 B CN103524963 B CN 103524963B
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Abstract
The invention provides a formula of a semiconductive internal shielding material for a scorch preventing cable. The formula is characterized by comprising the following components in parts by weight: 100 parts of a base material, 45-48 parts of conductive carbon black, 3-5 parts of a stripping agent, 5-8 parts of an antioxidant/metal deactivator, 4-6 parts of a crosslinking agent, 3-5 parts of an enhancer, 0.5-1 part of an anti-aging agent and 10-12 parts of a plasticizer. Through coordination of the components and the most appropriate content proportion of various components, the semiconductive internal shielding material provided by the invention obtains excellent mechanical performance, stripping performance, extrusion and scorch preventing performance, flame retardance, conductive performance and temperature stabilization performance.
Description
Technical field
The present invention relates to technical field of composite materials, a kind of formula of anti-incipient scorch cable semiconduction inner shield material is particularly provided.
Background technology
Wires and cables industry is electric power and the important supporting industry of the two large pillar industries in national economy that communicate, extremely important status is had in national economy, wherein industry production total amount accounts for 4 ‰ to 5 ‰ of the total GDP in the whole nation, electric wire product plays the vital role of the conveying energy, transmission of information, is national economy " blood vessel " and " nerve ".
Insulated cable is normally formed at conductor core wire outer cladding insulation layer, and it is well-known, in higher high-voltage dc, insulated cable is fine uneven owing to existing, easily cause the space between insulation layer and conductor and between insulation layer and internal shield that partial discharge phenomenon occurs, therefore for making the electric field distribution on cable insulation even, reduce the electric stress of insulation layer, thus prevent said corona discharge, usually need between its conductor and insulation layer, arrange semiconduction inner shield material.
Existing semiconduction inner shield material usually adopts and forms with like external shield material type, mainly add in the base-material of polymer composites there is certain conductivity graphitized carbon black, add other auxiliary materials to prepare again, but for the selection of base-material and auxiliary material, particularly for the formula of each composition, then not consensus, and these components and content thereof have very important impact for follow-up product preparation process and the product performance that finally obtain exactly.Such as base-material adopts ethylene-propylene rubber(EPR), material that polyvinyl chloride equimolecular quantity is higher, its carrying capacity for filler is poor, in addition the add-on of graphitized carbon black is large, thus cause the mobility of material be deteriorated and cause the follow-up difficulty extruding processing, and the vinyl-vinyl acetate copolymer generally used now as base-material then exist such as poor with insulation displacement, extrude and add VA decomposes and produce particle on surface and then affect the defects such as product performance in man-hour.Meanwhile, semiconduction inner shield material requirements is higher than external shield material, not only needs can all form the combination of level and smooth zero-clearance with core conductor and insulation layer, more will avoid the generation of incipient scorch phenomenon in the course of processing.
Therefore, obtain and a kind of there is the formula being exclusively used in semiconduction inner shield material of excellent and stable use properties and the complete processing adapted with it, there is important Research Significance and value.
Summary of the invention
Namely object of the present invention is to provide a kind of novel formula with the anti-incipient scorch semiconduction inner shield material of excellent and stable use properties.
The formula of the anti-incipient scorch semiconduction inner shield material in the present invention is as follows: with parts by weight, base-material 100 parts, graphitized carbon black 45-48 part, stripper 3-5 part, antioxygen/metal passivator 5-8 part, linking agent 4-6 part, toughener 3-5 part, anti-aging agent 0.5-1 part, softening agent 10-12 part
Described base-material is mixed by terpolymer EP rubber and vinyl-vinyl acetate copolymer, and the ratio of the two is terpolymer EP rubber: vinyl-vinyl acetate copolymer=1:5-7, the mooney viscosity (1+4) 125 DEG C of described terpolymer EP rubber is 20-25, and in described vinyl-vinyl acetate copolymer, the content of vinyl-acetic ester is 55-60%;
Described graphitized carbon black is the graphitized carbon black being mixed with multi-walled carbon nano-tubes, the iodine number of carbon black is 100-200mg/g, and median size is 70-100nm, DBP is 150-200cc/100g, the diameter of multi-walled carbon nano-tubes is 10-20nm, is 13-16% relative to the content of carbon black;
Described stripper is oxidized polyethlene wax;
Described antioxygen/metal passivator is four-[3-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and N, N '-bis-[β (3,5-di-tert-butyl-hydroxy phenyl) propionyl] hydrazine, the mass ratio of the two is 1:2;
Described toughener is four acicular type zinc oxide crystal whisker;
Described linking agent is dicumyl peroxide;
Described anti-aging agent is N-(1,3-dimethyl) butyl-N'-diphenyl-para-phenylene diamine;
Described softening agent is Zinic stearas.
Preferred further, terpolymer EP rubber in described base-material: vinyl-vinyl acetate copolymer=1:6; And the content of vinyl-acetic ester is 57% in vinyl-vinyl acetate copolymer;
Preferred further, described graphitized carbon black is 47 weight parts, and multi-walled carbon nano-tubes is 15% relative to the content of carbon black;
Preferred further, described oxidized polyethlene wax is 4 weight parts;
Preferred further, described antioxygen/metal passivator is 7 weight parts;
Preferred further, described dicumyl peroxide is 5 weight parts;
Preferred further, described four acicular type zinc oxide crystal whisker is 4 weight parts.
The reasonable design of the present invention formula of semiconduction inner shield material, by coordinative role and the content proportioning the most suitable of each component, obtain and there is excellent mechanical performance, stripping performance, extrude the semi-conductive shielding material of scorching quality, flame retardant properties, conductivity and temperature-stable performance.
Embodiment
Embodiment 1.
Undertaken preparing burden by each component proportion given by table 1 and each raw material is all dried to 100 DEG C for subsequent use; Then first plasticate to terpolymer EP rubber (A), when plasticating, control roller temperature is at 70 DEG C, and plasticate time 5-10min; By the order of vinyl-vinyl acetate copolymer (B), graphitized carbon black (C), softening agent (D), toughener (E), anti-aging agent (F), stripper (G), antioxygen/metal passivator (H), each raw material successively being added Banbury mixer subsequently carries out mixing, mixing temperature is 100-120 DEG C, and mixing time is 10-15min; Then put in Banbury mixer by the terpolymer EP rubber of plasticating and carry out melting mixing, melting temperature is 170-190 DEG C, and mixing time is 5-10min; Through single screw extrusion machine extruding pelletization after mixing discharging, enter high-speed kneading machine and spray linking agent (I) high-speed mixing, and control temperature is at 80-100 DEG C after granulation, after mixing 3-5min, cooling obtains product.Wherein terpolymer EP rubber: vinyl-vinyl acetate copolymer=1:6, the mooney viscosity (1+4) 125 DEG C of described terpolymer EP rubber is 21, in described vinyl-vinyl acetate copolymer, the content of vinyl-acetic ester is 57%, in described graphitized carbon black, the iodine number of carbon black is 150mg/g, median size is 80nm, DBP is 180cc/100g, and the diameter of multi-walled carbon nano-tubes is 15nm, is 15% relative to the content of carbon black.
Embodiment 2-3 and comparative example 1#-8# place formula as shown in table 1 outside, preparation method is all identical with embodiment 1.
Table 1
The performance parameter test of each embodiment is listed in table 2, wherein volume specific resistance is measured respectively under 23 DEG C and 90 DEG C of two temperature, squeeze cable incipient scorch to represent with zero (without incipient scorch phenomenon), △ (substantially without incipient scorch phenomenon), × (having incipient scorch phenomenon) three grades, peeling force is measured respectively under 25 DEG C and 50 DEG C of two temperature.As shown in Table 2:
The content of graphitized carbon black can not be too low, otherwise the wretched insufficiency of the conductivity of product can be caused, but can not be too high, otherwise the severe exacerbation of its volume specific resistance temperature stability can be caused, not only can cause the deterioration of the mechanical properties such as intensity, elongation and permanentset simultaneously, more can make the mobility severe exacerbation of system, affect extrusion performance, in crowded cable process generation incipient scorch phenomenon.The content of the graphitized carbon black in the present invention's formula should control at 45-48 weight part
The content of toughener four acicular type zinc oxide crystal whisker at least should reach 3 weight parts, otherwise the tensile strength of product will be not enough, particularly can cause the severe exacerbation of permanentset; But more than 5 weight parts, otherwise can not can cause the rising of system viscosity thus be unfavorable for processing characteristics, causing product mechanics penalty on the contrary, also easily occur incipient scorch phenomenon.
Adding of stripper has vital effect for system relative to the stripping performance of insulation layer, the acid value of polyethylene wax has material impact for the intermiscibility of itself and crosslinked polyethylene, and the oxidized polyethlene wax acid value selected in this formula is at 20-30mg KOH/g, poorer for the consistency of common crosslinked polyetylene insulated layer compared to common polyethylene wax, with terpolymer EP rubber and process in can obtain well and insulation layer at the stripping performance of normal temperature and high temperature, for giving full play to its effect, oxidized polyethlene wax be at least 3 weight parts, if but its content is more than 5 weight parts, does not affect too much for stripping performance, can add to the difficulties for the shaping of product on the contrary, incipient scorch is had to be inclined to.
Anti-oxidant/metal passivator four-[3-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and N, N '-bis-[β (3,5-di-tert-butyl-hydroxy phenyl) propionyl] hydrazine 1:2 select mainly consider its performance antioxidant while, more can play the effect preventing incipient scorch phenomenon from occurring, in order to play this effect, its content at least should be 5 weight parts, too much interpolation is too many effect not, can be cross-linked by extra-inhibitory on the contrary.Simultaneously, four-[3-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester to a certain extent can with four acicular type zinc oxide crystal whisker cooperative flame retardant well, but itself and N, N '-bis-[β (3,5-di-tert-butyl-hydroxy phenyl) propionyl] hydrazine is preferably 1:2, otherwise the two not only can not play collaborative oxidation resistant effect well, and also may cancel each other positively effect.
The content of linking agent should reach 4 weight parts, can make crosslinked abundant not, be difficult to the dispersion making carbon black full and uniform, thus cause the volume specific resistance of product too high, the plasticity of system also can be caused to worsen simultaneously lower than 4 weight parts.But the content of linking agent also should more than 6 weight parts, otherwise can not cause excessively crosslinked, makes product retractility severe exacerbation.
Table 2
The formula of embodiment 4 and 5 is except terpolymer EP rubber: the content that the ratio of vinyl-vinyl acetate copolymer is respectively vinyl-acetic ester in 1:5 and 1:7, the vinyl-vinyl acetate copolymer selected is respectively 55% and 60%, multi-walled carbon nano-tubes is respectively except 13% and 16% relative to the content of carbon black, and all the other are identical with embodiment 2; Comparatively speaking, terpolymer EP rubber in comparative example 9#: the ratio of vinyl-vinyl acetate copolymer is 1:4.5, in comparative example 10#-11#, in vinyl-vinyl acetate copolymer, the content of vinyl-acetic ester is respectively 50% and 65%, in comparative example 12#, multi-walled carbon nano-tubes is 10% relative to the content of carbon black, all the other are all identical with embodiment 2, and test result is as shown in table 3.
Table 3
As shown in Table 3, terpolymer EP rubber: the proportioning of vinyl-vinyl acetate copolymer must be suitable, too low terpolymer EP rubber content plays being difficult to the effect improving separability, if but its too high levels, then may worsen and extrude processing characteristics and cause incipient scorch, also can reduce mechanical property, thermotolerance etc. simultaneously.
In vinyl-vinyl acetate copolymer, the content of vinyl-acetic ester is also the important factor affecting separability, the too low then system of content of vinyl-acetic ester and the intermiscibility of insulation layer fine, and be difficult to peel off, its too high levels then can cause its softening temperature to reduce, thus high temperature separability is deteriorated.
Under the prerequisite of graphitized carbon black mass conservation, the interpolation of multi-walled carbon nano-tubes significantly improves the stability of volume specific resistance and its temperature, also there is certain improvement for mechanical property etc. simultaneously, for giving full play to the effect of multi-walled carbon nano-tubes, its content at least should be 13%, if but more than 16%, its effect also can't significantly change again.
For formula system of the present invention, terpolymer EP rubber must be plasticated through certain before mixing, could meet the requirement of extruding, but not easily too high, the time should not be long for the temperature of plasticating, otherwise affect its mixing behavior on the contrary, through summing up with roller temperature at 70 DEG C, the time 5-10min of plasticating is advisable; And system can be realized by the sequential feeds empirical tests of vinyl-vinyl acetate copolymer, graphitized carbon black, softening agent, toughener, anti-aging agent, stripper, anti-oxidant/metal passivator and mix the most uniformly; The temperature of melting mixing has at 170-190 DEG C the extrusion performance that flows preferably, and mixing time is not easily excessively of a specified duration, otherwise when easily causing extruding, precrosslink occurs; And to be verified be the selection the most suitable that can obtain the cross-linking properties that contains last mixing temperature and time.Through the formula of the present invention's design, be aided with described preparation technology parameter, can obtain and there is excellent mechanical performance, stripping performance, extrude the semiconduction inner shield material of scorching quality, conductivity and stability.
Claims (6)
1. an anti-incipient scorch semiconduction inner shield material, is characterized in that having following composition: with parts by weight, base-material 100 parts, graphitized carbon black 45-48 part, stripper 3-5 part, antioxygen/metal passivator 5-8 part, linking agent 4-6 part, toughener 3-5 part, anti-aging agent 0.5-1 part, softening agent 10-12 part
Described base-material is mixed by terpolymer EP rubber and vinyl-vinyl acetate copolymer, and the ratio of the two is terpolymer EP rubber: vinyl-vinyl acetate copolymer=1:5-7, the mooney viscosity (1+4) 125 DEG C of described terpolymer EP rubber is 20-25, and in described vinyl-vinyl acetate copolymer, the content of vinyl-acetic ester is 55-60%;
Described graphitized carbon black is the graphitized carbon black being mixed with multi-walled carbon nano-tubes, the iodine number of carbon black is 100-200mg/g, and median size is 70-100nm, DBP is 150-200cc/100g, the diameter of multi-walled carbon nano-tubes is 10-20nm, is 13-16% relative to the content of carbon black;
Described stripper is oxidized polyethlene wax;
Described antioxygen/metal passivator is four-[3-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and N, N '-bis-[β (3,5-di-tert-butyl-hydroxy phenyl) propionyl] hydrazine, the mass ratio of the two is 1:2;
Described toughener is four acicular type zinc oxide crystal whisker;
Described linking agent is dicumyl peroxide;
Described anti-aging agent is N-(1,3-dimethyl) butyl-N'-diphenyl-para-phenylene diamine;
Described softening agent is Zinic stearas.
2. anti-incipient scorch semiconduction inner shield material according to claim 1, is characterized in that: terpolymer EP rubber in described base-material: vinyl-vinyl acetate copolymer=1:6; And the content of vinyl-acetic ester is 57% in vinyl-vinyl acetate copolymer.
3. anti-incipient scorch semiconduction inner shield material according to claim 1, is characterized in that: described oxidized polyethlene wax is 4 weight parts.
4. anti-incipient scorch semiconduction inner shield material according to claim 1, is characterized in that: described antioxygen/metal passivator is 7 weight parts.
5. anti-incipient scorch semiconduction inner shield material according to claim 1, is characterized in that: described dicumyl peroxide is 5 weight parts.
6. anti-incipient scorch semiconduction inner shield material according to claim 1, is characterized in that: described four acicular type zinc oxide crystal whisker is 4 weight parts.
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| CN103819820A (en) * | 2014-02-10 | 2014-05-28 | 上海蓝昊电气江苏有限公司 | Mine cable rubber sheath conductor shielding material |
| JP6347415B2 (en) * | 2014-11-20 | 2018-06-27 | 日立金属株式会社 | Semiconductive resin composition and power transmission cable using the same |
| CN112750556A (en) * | 2020-12-22 | 2021-05-04 | 江苏乾锦塑业科技有限公司 | High-temperature-resistant CPVC cable protection insulating pipe and production process thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6251977B1 (en) * | 1998-06-11 | 2001-06-26 | Hutchinson | Elastomer composition based on EPDM, and a powder transmission belt made essentially out of said elastomer |
| CN102030950A (en) * | 2009-09-29 | 2011-04-27 | 深圳市沃尔核材股份有限公司 | Ethylene-propylene-diene rubber thermal shrinkable tube and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6251977B1 (en) * | 1998-06-11 | 2001-06-26 | Hutchinson | Elastomer composition based on EPDM, and a powder transmission belt made essentially out of said elastomer |
| CN102030950A (en) * | 2009-09-29 | 2011-04-27 | 深圳市沃尔核材股份有限公司 | Ethylene-propylene-diene rubber thermal shrinkable tube and preparation method thereof |
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