CN103554802A - Formula of strippable semiconductive outer shielding material for cable - Google Patents
Formula of strippable semiconductive outer shielding material for cable Download PDFInfo
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- CN103554802A CN103554802A CN201310507150.7A CN201310507150A CN103554802A CN 103554802 A CN103554802 A CN 103554802A CN 201310507150 A CN201310507150 A CN 201310507150A CN 103554802 A CN103554802 A CN 103554802A
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Abstract
The invention provides a formula of a strippable semiconductive outer shielding material. The formula is characterized by consisting of the following components in parts by weight: 100 parts of base material, 50-55 parts of conductive carbon black, 2-4 parts of stripping agent, 3-5 parts of antioxidant, 3-5 parts of crosslinking agent, 1-3 parts of reinforcing agent, 0.5-1 part of anti-aging agent and 10-12 parts of plasticizer. According to the semiconductive outer shielding material provided by the invention, through the coordination effect of the components and the optimal content proportions, excellent mechanical property, stripping property, flame retardance, conductivity and temperature stability are obtained.
Description
Technical field
The present invention relates to technical field of composite materials, the formula of a kind of peelable cable with semiconduction external shield material is particularly provided.
Background technology
Wires and cables industry is the important supporting industry of electric power and the two large pillar industries in national economy of communicating by letter, in national economy, there is extremely important status, 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 carrying the energy, transmission of information, is " blood vessel " and " nerve " of national economy.
Insulated cable normally forms 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 that partial discharge phenomenon occurs the space between insulation layer and conductor and between insulation layer and external shielding layer, therefore for to make the electric field distribution on cable insulation even, reduces the electric stress of insulation layer, thereby prevent said corona discharge, conventionally need to semiconduction external shield material be set at its outside surface.
Existing semiconduction external shield material is mainly in the base-material of polymer composites, to add to have the graphitized carbon black of certain conductivity, add other auxiliary materials to prepare again, but the selection for base-material and auxiliary material, particularly for the formula of each composition, consensus not, and these components and content thereof have very important impact for follow-up product preparation process and the product performance that finally obtain exactly.For example 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, thereby cause the mobility variation of material and cause the follow-up difficulty of extruding processing, and the vinyl-vinyl acetate copolymer generally using now as base-material 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.
Therefore, obtain a kind of formula of the semiconduction external shield material with excellent and stable use properties and the complete processing adapting with it, be that technician studies and improved emphasis always.
Summary of the invention
Object of the present invention is to provide a kind of formula of the novel strippable semi-conductive external shield material with excellent and stable use properties.
The formula of the strippable semi-conductive external shield material in the present invention is as follows: in weight part, and 100 parts of base-materials, graphitized carbon black 50-55 part, stripper 2-4 part, antioxidant 3-5 part, linking agent 3-5 part, toughener 1-3 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=1:3-5,125 ℃ of mooney viscosities of described terpolymer EP rubber (1+4) are 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 that is mixed with multi-walled carbon nano-tubes, the iodine number of carbon black is 100-200mg/g, and median size is 70-100nm, and DBP is 150-200cc/100g, the diameter of multi-walled carbon nano-tubes is 10-20nm, with respect to the content of carbon black, is 10-15%;
Described stripper is oxidized polyethlene wax;
Described antioxidant is four-[3-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters and poly-two (2-methyl-4-hydroxyl-5-tert.-butylbenzene) thioether, and the mass ratio of the two is 1:1;
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.
Further preferred, terpolymer EP rubber in described base-material: vinyl-vinyl acetate copolymer=1:4; And in vinyl-vinyl acetate copolymer, the content of vinyl-acetic ester is 57%;
Further preferred, described graphitized carbon black is 52 weight parts, and multi-walled carbon nano-tubes is 12% with respect to the content of carbon black;
Further preferred, described oxidized polyethlene wax is 3 weight parts;
Further preferred, described antioxidant is 4 weight parts;
Further preferred, described dicumyl peroxide is 4 weight parts;
Further preferred, described four acicular type zinc oxide crystal whisker is 2 weight parts.
Reasonable design of the present invention the formula of semiconduction external shield material, by the coordinative role of each component and the most suitable content proportioning, obtained there is excellent mechanical property, the semi-conductive shielding material of stripping performance, flame retardant properties, conductivity and temperature-stable performance.
Embodiment
Embodiment 1.
By each given component proportion of table 1 prepare burden and by each raw material all dry to 100 ℃ standby; Then first terpolymer EP rubber (A) is plasticated, while plasticating, control roller temperature is at 70 ℃, and time 5-10min plasticates; By the order of vinyl-vinyl acetate copolymer (B), graphitized carbon black (C), softening agent (D), toughener (E), anti-aging agent (F), stripper (G), antioxidant (H), successively add Banbury mixer to carry out each raw material subsequently mixing, mixing temperature is 100-120 ℃, and mixing time is 10-15min; Then the terpolymer EP rubber of plasticating is put in Banbury mixer and carried out melting mixing, melting temperature is 170-190 ℃, and mixing time is 5-10min; After mixing discharging, through single screw extrusion machine extruding pelletization, after granulation, enter high-speed kneading machine and spray linking agent (I) high-speed mixing, and control temperature at 80-100 ℃, the cooling product that obtains after mixing 3-5min.Terpolymer EP rubber: vinyl-vinyl acetate copolymer=1:4 wherein, 125 ℃ of mooney viscosities of described terpolymer EP rubber (1+4) are 23, 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, with respect to the content of carbon black, is 12%.
Outside embodiment 2-3 and comparative example 1#-9# place formula are as shown in table 1, preparation method is all identical with embodiment 1.
Table 1
The performance parameter test of each embodiment is listed in table 2, and wherein volume specific resistance is measured respectively at 23 ℃ and 90 ℃ of two temperature, and peeling force is measured respectively at 25 ℃ and 50 ℃ of two temperature.As shown in Table 2:
The content of graphitized carbon black can not be too low, otherwise the wretched insufficiency that can cause the conductivity of product, but can not be too high, otherwise can cause the severe exacerbation of its volume specific resistance temperature stability, also can cause the deterioration of the mechanical properties such as intensity, elongation and permanentset simultaneously.The content of the graphitized carbon black in the present invention's formula should be controlled at 50-55 weight part
The content of toughener four acicular type zinc oxide crystal whisker at least should reach 1 weight part, otherwise the tensile strength of product will be not enough, particularly can cause the severe exacerbation of permanentset; But had better not surpass 3 weight parts, thereby otherwise can cause that the rising of system viscosity is unfavorable for processing characteristics, cause on the contrary product mechanical property to worsen.
Adding for system of stripper has vital effect with respect 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 of selecting in this formula is at 20-30mg KOH/g, poorer for the consistency of common crosslinked polyetylene insulated layer than common polyethylene wax, in the process with terpolymer EP rubber use, 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 2 weight parts, if but its content surpasses 4 weight parts for the not too many impact of stripping performance, can add to the difficulties for the shaping of product on the contrary.
Antioxidant four-[3-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] to be 1:1 select mainly considers that it can bring into play cooperative flame retardant effect well with four acicular type zinc oxide crystal whisker for pentaerythritol ester and poly-two (2-methyl-4-hydroxyl-5-tert.-butylbenzene) thioether, and the effect of precrosslink is extruded in certain preventing, in order to bring into play this effect, its content at least should be 3 weight parts, when surpassing 5 weight part, flame retardant effect does not increase significantly, simultaneously may follow-up being cross-linked of severe inhibition.
The content of linking agent should reach 3 weight parts, can make crosslinked fully not lower than 3 weight parts, is difficult to the dispersion that makes carbon black full and uniform, thereby causes the volume specific resistance of product too high, also can cause the plasticity of system to worsen simultaneously.But the content of linking agent is should exceed 5 weight parts not also, otherwise can cause excessively crosslinkedly, make product retractility severe exacerbation.
Table 2
Embodiment 4 and 5 formula are except terpolymer EP rubber: in the vinyl-vinyl acetate copolymer that the ratio of vinyl-vinyl acetate copolymer is respectively 1:3 and 1:5, select, the content of vinyl-acetic ester is respectively 55% and 60%, multi-walled carbon nano-tubes is respectively 10% and 15% with respect to the content of carbon black, and all the other are identical with embodiment 2; Comparatively speaking, terpolymer EP rubber in comparative example 10#: the ratio of vinyl-vinyl acetate copolymer is 1:5.5, in comparative example 11#-12#, in vinyl-vinyl acetate copolymer, the content of vinyl-acetic ester is respectively 50% and 65%, in comparative example 13#, multi-walled carbon nano-tubes is 5% with respect 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 is by being difficult to the effect of performance raising separability, if but its too high levels may worsen mechanical property, thermotolerance etc.
In vinyl-vinyl acetate copolymer, the content of vinyl-acetic ester is also the important factor that affects separability, the too low system of content of vinyl-acetic ester and the intermiscibility of insulation layer are fine, and be difficult to peel off, its too high levels can cause its softening temperature to reduce, thereby makes high temperature separability variation.
Under the prerequisite of graphitized carbon black mass conservation, the interpolation of multi-walled carbon nano-tubes obviously improved volume specific resistance with and the stability of temperature, simultaneously for mechanical property etc., also there is certain improvement, for giving full play to the effect of multi-walled carbon nano-tubes, its content at least should be 5%, if but surpassed 15%, its effect also could significantly change again.
For formula system of the present invention, terpolymer EP rubber must, in certain the plasticating of mixing front process, could meet the requirement of extruding, but that the temperature of plasticating is difficult for is too high, the time is unsuitable long, otherwise affect on the contrary its mixing behavior, through summing up with roller temperature at 70 ℃, the time 5-10min of plasticating is advisable; And can realize system by the reinforced empirical tests of the order of vinyl-vinyl acetate copolymer, graphitized carbon black, softening agent, toughener, anti-aging agent, stripper, antioxidant, mix the most uniformly; The temperature of melting mixing has at 170-190 ℃ the extrusion performance that flows preferably, and mixing time was difficult for of a specified duration, otherwise precrosslink occurs while easily causing extruding; And to be verified be the most suitable selection that can obtain the cross-linking properties containing last mixing temperature and time.Through the formula of the present invention's design, be aided with described preparation technology parameter, can obtain the strippable semi-conductive external shield material with excellent mechanical property, stripping performance, flame retardant properties, conductivity and stability.
Claims (7)
1. a formula for strippable semi-conductive external shield material, is characterized in that having following composition: in weight part, and 100 parts of base-materials, graphitized carbon black 50-55 part, stripper 2-4 part, antioxidant 3-5 part, linking agent 3-5 part, toughener 1-3 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=1:3-5,125 ℃ of mooney viscosities of described terpolymer EP rubber (1+4) are 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 that is mixed with multi-walled carbon nano-tubes, the iodine number of carbon black is 100-200mg/g, and median size is 70-100nm, and DBP is 150-200cc/100g, the diameter of multi-walled carbon nano-tubes is 10-20nm, with respect to the content of carbon black, is 10-15%;
Described stripper is oxidized polyethlene wax;
Described antioxidant is four-[3-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters and poly-two (2-methyl-4-hydroxyl-5-tert.-butylbenzene) thioether, and the mass ratio of the two is 1:1;
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. formula according to claim 1, is characterized in that: terpolymer EP rubber in described base-material: vinyl-vinyl acetate copolymer=1:4; And in vinyl-vinyl acetate copolymer, the content of vinyl-acetic ester is 57%.
3. formula according to claim 1, is characterized in that: described graphitized carbon black is 52 weight parts, and multi-walled carbon nano-tubes is 12% with respect to the content of carbon black.
4. formula according to claim 1, is characterized in that: described oxidized polyethlene wax is 3 weight parts.
5. formula according to claim 1, is characterized in that: described antioxidant is 4 weight parts.
6. formula according to claim 1, is characterized in that: described dicumyl peroxide is 4 weight parts.
7. formula according to claim 1, is characterized in that: described four acicular type zinc oxide crystal whisker is 2 weight parts.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105778345A (en) * | 2016-04-15 | 2016-07-20 | 安徽华联电缆集团有限公司 | Formula of flame-retardant shielding cable material and preparation method of flame-retardant shielding cable material |
| JP2018028031A (en) * | 2016-08-19 | 2018-02-22 | 東洋インキＳｃホールディングス株式会社 | Conductive resin composition, molded article, and method for producing the same |
| CN109320894A (en) * | 2018-09-30 | 2019-02-12 | 远东电缆有限公司 | Silane-crosslinkable strippable semi-conductive external shield material and preparation method thereof |
| CN109627563A (en) * | 2018-12-25 | 2019-04-16 | 江苏东方电缆材料有限公司 | A kind of easily peelable EVA/POP semiconductive external shield material |
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| US20090075088A1 (en) * | 2007-07-20 | 2009-03-19 | Advanced Ceramics Research, Inc. | Lightning strike mitigation composites |
| CN101891915A (en) * | 2010-07-06 | 2010-11-24 | 苏州市双鑫新材料科技有限公司 | Strippable semi-conductive shielding material for insulation of cross-linked cable |
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| US20090075088A1 (en) * | 2007-07-20 | 2009-03-19 | Advanced Ceramics Research, Inc. | Lightning strike mitigation composites |
| CN101891915A (en) * | 2010-07-06 | 2010-11-24 | 苏州市双鑫新材料科技有限公司 | Strippable semi-conductive shielding material for insulation of cross-linked cable |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105778345A (en) * | 2016-04-15 | 2016-07-20 | 安徽华联电缆集团有限公司 | Formula of flame-retardant shielding cable material and preparation method of flame-retardant shielding cable material |
| JP2018028031A (en) * | 2016-08-19 | 2018-02-22 | 東洋インキＳｃホールディングス株式会社 | Conductive resin composition, molded article, and method for producing the same |
| CN109320894A (en) * | 2018-09-30 | 2019-02-12 | 远东电缆有限公司 | Silane-crosslinkable strippable semi-conductive external shield material and preparation method thereof |
| CN109627563A (en) * | 2018-12-25 | 2019-04-16 | 江苏东方电缆材料有限公司 | A kind of easily peelable EVA/POP semiconductive external shield material |
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