CN105400131A - A composite material used for a special cable, a preparing method thereof and the special cable - Google Patents

A composite material used for a special cable, a preparing method thereof and the special cable Download PDF

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Publication number
CN105400131A
CN105400131A CN201510915461.6A CN201510915461A CN105400131A CN 105400131 A CN105400131 A CN 105400131A CN 201510915461 A CN201510915461 A CN 201510915461A CN 105400131 A CN105400131 A CN 105400131A
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special cable
coupling agent
vinyl acetate
acetate copolymer
ethene
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CN105400131B (en
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唐思钊
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YANCHENG KEHENGDA MATERIALS CO., LTD.
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唐思钊
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A30/00Adapting or protecting infrastructure or their operation
    • Y02A30/14Extreme weather resilient electric power supply systems, e.g. strengthening power lines or underground power cables

Abstract

A composite material used for a special cable, a preparing method thereof and the special cable are disclosed. According to the composite material, polyether ether ketone, polyethylene and polyimide are mixed according to a ratio and adopted as a substrate material, ethylene-vinyl acetate copolymer modified geopolymers, molybdenum trioxide and magnesium oxide are processed by a coupling agent and then adopted as a flame retardant additive, dicumyl peroxide is adopted as a crosslinking catalyst, silicon nitride whiskers are adopted as a fortifier, and the composite material is formed by melting and blending. The composite material has good high-temperature resistance and improved flame retardant effects, and can achieve no performance stability decrease under severe working conditions. In addition, the composite material is used for preparing an outer sheath of the special cable, and durability, fire resistance and stability of the special cable are improved.

Description

A kind of special cable matrix material, its preparation method and special cable
Technical field
The invention belongs to power cable field, particularly a kind of special cable matrix material, its preparation method and apply its special cable prepared.
Background technology
Along with the increasing extent of power cable application is wide, different environment for use has different requirement, e.g., and high temperature resistant, low temperature resistant, oil resistant, anti tear, fire-retardant, anti-animal damage etc.Particularly under, applied environment complicated situation special in working conditions, the demand day of special cable is aobvious outstanding, has higher requirement to the reliability of cable, wearing quality.
Common special cable has: fireproof cable, heating cable, environment-friendly cable etc.In prior art, according to the demand of special cable, new texture, novel material, novel process is often adopted to prepare the special cable being formed and be applicable to demand.Along with the development of technology, at Material Field, traditional cable material, such as, polyethylene, polypropylene, polyvinyl chloride, silicon rubber, fluoroplastics etc., the needs meeting reality are difficult to, such as, when tradition contains the burning of the fire-resistant cable material of halogen family fire retardant, a large amount of smog and hydrogen halide can be produced, cause personnel to withdraw and be difficult to launch with fire-fighting work, cause casualties and property damage, the smog that cable fire produces and hydrogen chloride gas are also cause huge pollution to environment simultaneously.To flame retardant cable in the amount of smoke of being heated and combustion case produces, International Electrotechnical Commission IEC61034 defines cable fire smoke density measuring method, Chinese market requires that the minimum transmittance that burning produces smog must not should be not more than 100mg/g lower than defining equally in 30%, IEC60754-1 the flame retardant cable hydrogen chloride gas scale of construction discharged of burning.
Along with the development of technology, domestic also have special cable material study widely, and propose corresponding solution.Wherein topmost solution concentrate on to traditional material composite modified on.Such as, patent CN103865203 provides a kind of formula improving PVC insulating material insulating property, adds the magnesium hydroxide etc. that surface uses barium oxide process, improve insulating property in polyvinyl chloride resin.But the material of its still a kind of Halogen all the time, does not fundamentally abandon Halogen material.And for example, patent CN104086716A discloses a kind of high-temperature-resistant special cable modified poly ethylene sheath material, by by high-temperature-resistant special cable material new to metallocene linear-low density polyethylene, polystyrene, the blended formation of PEEK, improve the performances such as wear-resisting, shock-resistant, tear-resistant, radioprotective.It is evenly blended more difficult to be formed between above-mentioned polymkeric substance, require comparatively complicated, and its auxiliary agent added is more, adds product cost undoubtedly, reduces the reliability of cable to preparation technology.Same, CN104292601A provides a kind of oil-resistant low-smoke halogen-free flame-retardant CABLE MATERIALS, by the mixing of ethylene-vinyl acetate copolymer, Low Density Polyethylene, sulphurated siliastic, polymeric amide etc., improves the performance of conventional polyolefins blend composition.
Visible, for overcoming many defects of the prior art, the special cable matrix material needing a kind of high temperature resistant, fire-retardant, that shielding system energy is good reliability badly high substitutes traditional cable material.
Summary of the invention
The present invention is intended to solve but be not limited to following technical problem: improve the high temperature resistant character of special cable matrix material, improve flame retardant effect, improve shielding properties, improve wearing quality and the reliability of special cable, guarantee that the stability under bad working environments does not reduce.
For solving the problems of the technologies described above, the present invention provide firstly a kind of special cable matrix material, comprises following composition, counts by weight:
Polyether-ether-ketone 45-65
Polyethylene 15-30
Polyimide 10-20
Ethene-vinyl acetate copolymer modification ground polymers 4-8
Silicon nitride crystal whisker 2-5
Molybdic oxide 0.5-2.5
Magnesium oxide 1-20
Coupling agent 0.1-1.5
Dicumyl peroxide 0.3-0.8.
For making heat-resisting, fire prevention, low temperature resistant, shock resistance improves, and high performance engineering polyether-ether-ketone, polyethylene and polyimide are carried out compound and carry out corresponding modification significantly promoting its performance as special cable matrix material by the present invention in proportion.Especially, have employed ethene-vinyl acetate copolymer over the ground polymers carried out modification, it can be used as additive to add, effectively raise fire resistance and wear resisting property.It is pointed out that ground polymers and geopolymer, express for two kinds and be conventional expression in the art, there is no other particular meanings, think that this area is extensively studied and the title approved.In addition, introduce dicumyl peroxide, as initiator, to poly crosslinked particularly effective, therefore, be not simple physical mixed in above-mentioned mixing of materials process, but with the chemically crosslinked process of certain degree, and this cross-linking process is not limited to being cross-linked between Polyethylene Chain, and contingent any reaction in above-mentioned raw materials should be interpreted as widely.
Optionally, the molybdic oxide median size adopted is 30-200nm, molybdic oxide at material once burning, to the formation of flue gas, there is effective restraining effect, and its particle diameter is adjusted, be not only related to its inhibition to flue gas, simultaneously, contriver also finds, also has impact to the mechanical property after forming materials.
Magnesium oxide is as fire resistant infilling, be widely applied in special cable matrix material, but, adopt the mode of gradient particle diameter filler to improve magnesium oxide particle distribution in the composite and on the impact of the mechanical property of matrix but not by disclosed in prior art or enlightenment, contriver finds that the magnesium oxide of employing two kinds of size distribution carries out suitable proportioning, the mechanical quality of body material is increased, fire performance can't affect to some extent simultaneously, preferably, adopt the magnesium oxide of following proportioning as filler:
Magnesium oxide 20 ~ the 40wt% of 50nm≤median size≤300nm
Magnesium oxide 60 ~ the 80wt% of 300nm < median size≤1000nm.
For improving the consistency of mineral filler in polymeric matrix, adopt coupling agent as increase-volume auxiliary agent, described coupling agent is preferably the mixture of silane coupling agent and titanate coupling agent, in mass ratio, and silane coupling agent: titanate coupling agent=1 ~ 5:1.
For improving the comprehensive fire performance of ground polymers, and prevent it from the course of processing, forming reunion point, the ethene-vinyl acetate copolymer modification ground polymers that the present invention adopts is prepared by following methods:
(1) raw mixture is configured by mass percentage, metakaolin: sodium hydroxide: water glass: water=100:(10 ~ 20): (100 ~ 120): (500 ~ 2000); Raw mixture is incubated 5 ~ 20 hours at 50 ~ 70 DEG C, and spraying dry forms ground polymers powder;
(2) ethene-vinyl acetate copolymer modification ground polymers by ground polymers powder, silane coupling agent, ethene-vinyl acetate copolymer in mass ratio: 100:(0.5 ~ 1.5): (15 ~ 35) are melting mixing 10 ~ 20min at 80 ~ 90 DEG C, is formed.
Secondly, the invention provides a kind of preparation method of special cable matrix material, the composition of this matrix material is:
Count by weight:
Polyether-ether-ketone 45-65
Polyethylene 15-30
Polyimide 10-20
Ethene-vinyl acetate copolymer modification ground polymers 4-8
Silicon nitride crystal whisker 2-5
Molybdic oxide 0.5-2.5
Magnesium oxide 1-20
Coupling agent 0.1-1.5
Dicumyl peroxide 0.3-0.8.
Wherein, the size of magnesium oxide, molybdic oxide and materials, and the selecting of coupling agent, can select see foregoing.
Specifically comprise the following steps:
S1. the preparation of ethene-vinyl acetate copolymer modification ground polymers
(1) raw mixture is configured by mass percentage, metakaolin: sodium hydroxide: water glass: water=100:(10 ~ 20): (100 ~ 120): (500 ~ 2000); Raw mixture is incubated 1 ~ 3 hour at 50 ~ 70 DEG C, and spraying dry forms ground polymers powder;
(2) ethene-vinyl acetate copolymer modification ground polymers by ground polymers powder, silane coupling agent, ethene-vinyl acetate copolymer in mass ratio: 100:(0.5 ~ 1.5): (15 ~ 35) are melting mixing 10 ~ 20min at 80 ~ 90 DEG C, is formed;
S2. mineral filler modification
Silicon nitride crystal whisker, molybdic oxide, magnesium oxide, coupling agent are mixed in proportion formation mixture, by gained mixture and Virahol in mass ratio 1:2 carry out supersound process 10 ~ 50min after mixing, through suction filtration, washing, dryly obtain modified mineral filler;
S3. the preparation of special cable matrix material
Polyether-ether-ketone, polyethylene, polyimide, ethene-vinyl acetate copolymer modification ground polymers, dicumyl peroxide, modified mineral filler are mixed in proportion in high-speed mixer; extrude through twin screw extruder melt blending, obtain special cable matrix material through dicing machine granulation.
For improving into material homogeneity, melt blending extrusion temperature is 190 ~ 260 DEG C, and screw speed is 150 ~ 200rpm.
Again, present invention also offers a kind of special cable, comprise oversheath, brea bed, armor layer, insulation layer, screen layer and core wire accommodating cavity that ecto-entad is formed successively, regular polygon bracing frame is provided with in described core wire accommodating cavity, described regular polygon bracing frame is arranged along interval, cable length direction, described regular polygon bracing frame forms stiffening web from center to drift angle, core wire is by arranging through the space each stiffening web of regular polygon bracing frame, and described oversheath is made up of the above-mentioned special cable matrix material provided.
According to need of production, described regular polygon is regular hexagon or octagon, but is not limited to these two kinds selections, it is to be noted, the setting of stiffening web, necessarily all centers all do not form stiffening web to drift angle, rationally can arrange according to the requirement of actual ultimate compression strength.
Under normal circumstances, described core wire comprises plain conductor and coated insulation layer; Described core wire accommodating cavity is also filled with light-weight refractory fibrous packing to improve resistance to compression, tensile strength and fire performance, and selecting of light-weight refractory fiber is not particularly limited to, any materials known for those skilled in the art that this area can be adopted to commonly use.
The present invention is compared to the beneficial effect of prior art: special cable matrix material provided by the invention have employed, high performance engineering polyether-ether-ketone, polyethylene and composite polyimide material, and carry out corresponding modification and significantly can promote its performance as special cable matrix material.From detected result, it is heat-resisting, ageing resistance significantly improves: ultimate tensile strength reaches 22.6Mpa, and elongation at break is maximum more than 500%, after burin-in process, tensile strength velocity of variation is on average about-11.4%, and the elongation at break average rate of change is about 15.35%.Modification ground polymers and molybdic oxide and magnesium oxide act synergisticallys, and while ensureing the mechanical performance of matrix material, improve the fire performance of matrix material, after testing, the smoke density of prepared material is all less than 30Dm, and oxygen index is all greater than 30.Visible, this matrix material has the flame retardant effect of good high temperature resistant character, improvement, and the stability that can realize under bad working environments does not reduce.
Accompanying drawing explanation
Fig. 1 is the structural representation of special cable in embodiment 2-1.
Fig. 2 is the structural representation of special cable in embodiment 2-2.
Embodiment
For making technical scheme of the present invention and technique effect thereof clearly, clearly, below embodiment and comparative example the specific embodiment of the invention is further described.Should be appreciated that following embodiment is only the better embodiment of technical solution of the present invention, be not intended to limit the present invention.
(1) preparation of related raw material
The preparation of ethene-vinyl acetate copolymer modification ground polymers, adopt and carry out with the following method:
(1) raw mixture is configured by mass percentage, metakaolin: sodium hydroxide: water glass: water=100:10:110:1500; Raw mixture is incubated 1 hour at 60 DEG C, and spraying dry forms ground polymers powder;
(2) by ground polymers powder, silane coupling agent, ethene-vinyl acetate copolymer in mass ratio: 100:1.5:25 is melting mixing 15min at 80 DEG C, ethene-vinyl acetate copolymer modification ground polymers is formed, as raw material used in following examples.
(2) preparation of special cable matrix material
Embodiment 1-1
Raw material (by weight) is prepared by following ratio:
Polyether-ether-ketone 65
Polyethylene 20
Polyimide 20
Ethene-vinyl acetate copolymer modification ground polymers 8
Silicon nitride crystal whisker 4
Molybdic oxide 1.5
Magnesium oxide 15
Coupling agent 1.2
Dicumyl peroxide 0.6.
Wherein, molybdic oxide median size selects 100nm, and magnesium oxide selects the median size of 20wt% to be the magnesium oxide of 150nm and the median size of 80wt% to be the magnesian mixture of 500nm, and silane coupling agent selected by coupling agent: titanate coupling agent=2:1.
(1) silicon nitride crystal whisker, molybdic oxide, magnesium oxide, coupling agent are mixed in proportion formation mixture, by gained mixture and Virahol in mass ratio 1:2 carry out supersound process 30min after mixing, through suction filtration, washing, dryly obtain modified mineral filler;
(2) polyether-ether-ketone, polyethylene, polyimide, ethene-vinyl acetate copolymer modification ground polymers, dicumyl peroxide, modified mineral filler are mixed in proportion in high-speed mixer; extrude through twin screw extruder melt blending; melt blending extrusion temperature is 260 DEG C; screw speed is 150rpm; obtain special cable matrix material through dicing machine granulation, be designated as sample 1-1.
Embodiment 1-2
Compared to embodiment 1-1, only proportioning raw materials is adjusted as follows:
Count by weight:
Polyether-ether-ketone 45
Polyethylene 30
Polyimide 10
Ethene-vinyl acetate copolymer modification ground polymers 8
Silicon nitride crystal whisker 5
Molybdic oxide 1.5
Magnesium oxide 15
Coupling agent 1.3
Dicumyl peroxide 0.8.
Wherein, molybdic oxide median size selects 100nm, and magnesium oxide selects the median size of 20wt% to be the magnesium oxide of 150nm and the median size of 80wt% to be the magnesian mixture of 500nm, and silane coupling agent selected by coupling agent: titanate coupling agent=2:1.
Through the special cable matrix material that preparation is formed, be designated as sample 1-2.
Embodiment 1-3
Compared to embodiment 1-1, only proportioning raw materials is adjusted as follows:
Count by weight:
Polyether-ether-ketone 55
Polyethylene 15
Polyimide 15
Ethene-vinyl acetate copolymer modification ground polymers 8
Silicon nitride crystal whisker 2
Molybdic oxide 2.5
Magnesium oxide 10
Coupling agent 0.8
Dicumyl peroxide 0.4.
Wherein, molybdic oxide median size selects 150nm, and magnesium oxide selects the median size of 40wt% to be the magnesium oxide of 250nm and the median size of 60wt% to be the magnesian mixture of 800nm, and silane coupling agent selected by coupling agent: titanate coupling agent=2:1.
Through the special cable matrix material that preparation is formed, be designated as sample 1-3.
Embodiment 1-4
Compared to embodiment 1-1, only proportioning raw materials is adjusted as follows:
Polyether-ether-ketone 65
Polyethylene 20
Polyimide 20
Ethene-vinyl acetate copolymer modification ground polymers 8
Silicon nitride crystal whisker 4
Molybdic oxide 1.5
Magnesium oxide 15
Coupling agent 1.2
Dicumyl peroxide 0.6.
Wherein, molybdic oxide median size selects 100nm, and magnesium oxide selects median size to be the magnesium oxide of 200nm, and silane coupling agent selected by coupling agent: titanate coupling agent=2:1.
Through the special cable matrix material that preparation is formed, be designated as sample 1-4.
Embodiment 1-5
Compared to embodiment 1-1, only proportioning raw materials is adjusted as follows:
Polyether-ether-ketone 65
Polyethylene 20
Polyimide 20
Ethene-vinyl acetate copolymer modification ground polymers 8
Silicon nitride crystal whisker 4
Molybdic oxide 1.5
Magnesium oxide 15
Coupling agent 1.2
Dicumyl peroxide 0.6.
Wherein, molybdic oxide median size selects 100nm, and magnesium oxide selects median size to be the magnesium oxide of 600nm, and silane coupling agent selected by coupling agent: titanate coupling agent=2:1.
Through the special cable matrix material that preparation is formed, be designated as sample 1-5.
Embodiment 1-6
Compared to embodiment 1-1, only proportioning raw materials is adjusted as follows:
Polyether-ether-ketone 65
Polyethylene 20
Polyimide 20
Ethene-vinyl acetate copolymer modification ground polymers 4
Silicon nitride crystal whisker 4
Molybdic oxide 1.5
Magnesium oxide 15
Coupling agent 1.2
Dicumyl peroxide 0.6.
Wherein, molybdic oxide median size selects 100nm, and magnesium oxide selects the median size of 20wt% to be the magnesium oxide of 150nm and the median size of 80wt% to be the magnesian mixture of 500nm, and silane coupling agent selected by coupling agent: titanate coupling agent=2:1.
Through the special cable matrix material that preparation is formed, be designated as sample 1-6.
(3) performance test of special cable matrix material
Carry out dependence test to sample 1-1 to sample 1-6 according to the related request of GB/T2951.11-2008 and the relevant test method of flame retardant cable smoke density, test result is in table 1.
Table 1. properties of sample test result data table
Sample 1-1 1-2 1-3 1-4 1-5 1-6
Tensile strength/Mpa 22.6 20.8 20.2 21.0 20.5 22.4
Elongation at break/% 537 497 489 518 507 548
Aging back draft change rate of strength/% -7.8 -13.6 -12.8 -11.6 -12.1 -10.6
Aging rear elongation at break velocity of variation/% 12.3 15.4 16.5 14.9 17.3 15.7
Smoke density/Dm 14 15 14 23 21 26
Oxygen index/% 57 43 43 45 48 39
As can be seen from Table 1, special cable matrix material ultimate tensile strength provided by the invention reaches 22.6Mpa, elongation at break is maximum more than 500%, after burin-in process, tensile strength velocity of variation is on average about-11.4%, the elongation at break average rate of change is about 15.35%, and smoke density is all less than 30Dm, and oxygen index is all greater than 30.From These parameters, above-mentioned materials has the flame retardant effect of good high temperature resistant character, improvement, and the stability that can realize under bad working environments does not reduce.
(4) manufacture of special cable
Embodiment 2-1
With reference to Fig. 1, present embodiments provide a kind of special cable, comprise the oversheath 1 that ecto-entad is formed successively, brea bed 2, armor layer 3, insulation layer 4, screen layer 5 and core wire accommodating cavity 6, regular hexagon bracing frame 7 is provided with in described core wire accommodating cavity 6, described regular hexagon bracing frame 7 is arranged along interval, cable length direction, described regular hexagon bracing frame 7 forms stiffening web 8 from center to drift angle, core wire 9 is by arranging through the space each stiffening web of regular hexagon bracing frame 7, three are employed in the present embodiment, the special cable matrix material that described oversheath 1 is provided by above-described embodiment 1-1 is made.Described core wire 9 comprises plain conductor 10 and coated insulation layer 11; Described core wire accommodating cavity is also filled with light-weight refractory fibrous packing to improve resistance to compression, tensile strength and fire performance.
Embodiment 2-2
With reference to Fig. 2, with embodiment 2-1 unlike, adopt octagon bracing frame to substitute regular hexagon bracing frame in the present embodiment.

Claims (7)

1. a special cable matrix material, is characterized in that, comprises following composition, counts by weight:
Polyether-ether-ketone 45-65
Polyethylene 15-30
Polyimide 10-20
Ethene-vinyl acetate copolymer modification ground polymers 4-8
Silicon nitride crystal whisker 2-5
Molybdic oxide 0.5-2.5
Magnesium oxide 1-20
Coupling agent 0.1-1.5
Dicumyl peroxide 0.3-0.8.
2. special cable matrix material according to claim 1, is characterized in that, described molybdic oxide median size is about 30-200nm.
3. a preparation method for the special cable matrix material as described in any one of claim 1-3, is characterized in that, comprise the following steps:
S1. the preparation of ethene-vinyl acetate copolymer modification ground polymers
(1) raw mixture is configured by mass percentage, metakaolin: sodium hydroxide: water glass: water=100:(10 ~ 20): (100 ~ 120): (500 ~ 2000); Raw mixture is incubated 1 ~ 3 hour at 50 ~ 70 DEG C, and spraying dry forms ground polymers powder;
(2) ethene-vinyl acetate copolymer modification ground polymers by ground polymers powder, silane coupling agent, ethene-vinyl acetate copolymer in mass ratio: 100:(0.5 ~ 1.5): (15 ~ 35) are melting mixing about 10 ~ 20min at 80 ~ 90 DEG C, is formed;
S2. mineral filler modification
Silicon nitride crystal whisker, molybdic oxide, magnesium oxide, coupling agent are mixed in proportion formation mixture, by gained mixture and Virahol in mass ratio 1:2 carry out supersound process 10 ~ 50min after mixing, through suction filtration, washing, dryly obtain modified mineral filler;
S3. the preparation of special cable matrix material
Polyether-ether-ketone, polyethylene, polyimide, ethene-vinyl acetate copolymer modification ground polymers, dicumyl peroxide, modified mineral filler are mixed in proportion in high-speed mixer; extrude through twin screw extruder melt blending, obtain special cable matrix material through dicing machine granulation.
4. a special cable, it is characterized in that, comprise oversheath, brea bed, armor layer, insulation layer, screen layer and core wire accommodating cavity that ecto-entad is formed successively, regular polygon bracing frame is provided with in described core wire accommodating cavity, described regular polygon bracing frame is arranged along interval, cable length direction, described regular polygon bracing frame forms stiffening web from center to drift angle, core wire is by arranging through the space each stiffening web of regular polygon bracing frame, and described oversheath is made up of the special cable matrix material described in any one of claim 1-2.
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CN106782803B (en) * 2016-12-23 2018-08-28 安徽天元电缆有限公司 A kind of communal facility special cable
CN106782803A (en) * 2016-12-23 2017-05-31 安徽天元电缆有限公司 A kind of communal facility special cable
CN106898862A (en) * 2017-03-24 2017-06-27 桥运精密部件(苏州)有限公司 A kind of car antenna STAINLESS STEEL WIRE
CN108735364A (en) * 2018-05-28 2018-11-02 安徽徽宁电器仪表集团有限公司 A kind of fire-resistant composite cable peculiar to vessel
CN108795043A (en) * 2018-05-31 2018-11-13 芜湖卓越线束系统有限公司 A kind of new-energy automobile Insulation anticorrosive wire harness sheath material and preparation method thereof
CN108623992A (en) * 2018-05-31 2018-10-09 芜湖卓越线束系统有限公司 A kind of fire-retardant wire harness sheath material of new-energy automobile and preparation method thereof
CN108707333A (en) * 2018-05-31 2018-10-26 芜湖卓越线束系统有限公司 A kind of new-energy automobile high-low temperature resistant wire harness sheath material and preparation method thereof

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