CN103849084B - Waterproof flame retardant restrictive coating and manufacturing process thereof for cable - Google Patents

Waterproof flame retardant restrictive coating and manufacturing process thereof for cable Download PDF

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CN103849084B
CN103849084B CN201210512702.9A CN201210512702A CN103849084B CN 103849084 B CN103849084 B CN 103849084B CN 201210512702 A CN201210512702 A CN 201210512702A CN 103849084 B CN103849084 B CN 103849084B
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parts
flame retardant
waterproof flame
restrictive coating
cable
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CN103849084A (en
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程晓松
张贤灵
于德宝
孙玉萍
王小菲
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Suzhou Hengli Communications Material Co Ltd
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Suzhou Hengli Communications Material Co Ltd
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    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06Homopolymers or copolymers of vinyl chloride
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    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
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    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08L2201/00Properties
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    • C08L2203/00Applications
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    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend

Abstract

A kind of waterproof flame retardant restrictive coating for cable of the present invention and manufacturing process thereof, described waterproof flame retardant PVC cable material is made up of the component of following weight portion: polrvinyl chloride 100 parts, trioctyl trimellitate (TOTM) 20 ~ 30 parts, phthalic acid isodecyl ester 15 ~ 25 parts, environmental protection calcium-zinc composite stabilizing agent 5 ~ 10 parts, compound rare-earth stabilizer 5 ~ 10 parts, antimony oxide 4 ~ 8 parts, lubricant 0.3 ~ 1 part, 0.1 ~ 0.5 part of antioxidant, nano barium sulfate 3.5 ~ 7 parts, calcined kaolin 2.6 ~ 5.2 parts, nano silicon 3.5 ~ 7 parts, silane coupler 0.18 ~ 0.36 part;Described silane coupler is vinyl three ('beta '-methoxy ethyoxyl) silane, vinyltrimethoxy silane or γ-glycidyl ether oxygen propyl trimethoxy silicane.The present invention greatly reduces the water absorption of the coat layer of power cable, and product uses under moist or water-immerged environment, further increases electric property stable, does not the most produce change, improves the compactness of product, gets rid of material micropore.

Description

Waterproof flame retardant restrictive coating and manufacturing process thereof for cable
Technical field
The present invention relates to a kind of flame retardant sheath layer and preparation technology thereof, particularly relate to a kind of waterproof flame retardant for cable and protect Jacket layer and manufacturing process thereof.
Background technology
PVC cable insulating material is one of general synthetic plastic, is the second largest plastics being only second to polyethylene at present in the world Kind.Polyvinyl chloride cable material is simple owing to having good mechanical and physical performance, electric property, and processing technique, processability Can be excellent, price is relatively low, occupy prostatitis in CABLE MATERIALS industry total amount always, is widely used.PVC cable material is low in being generally used for The products such as pressure, data communication class cable, general purpose electric wire product, PVC cable material disclosure satisfy that insulation, sheath substantially Demand.But being as the extension of electric wire application scenario, the requirement to PVC cable material improves constantly, at the water-fast electric insulation of PVC In performance, always one difficult point, it is difficult to for a long time solve.
Polyvinyl chloride resin itself has excellent water resistance, but must add all kinds of plasticizer owing to CABLE MATERIALS produces, stablize Agent, all kinds of filler (potter's clay, calcium carbonate etc.), inevitably reduce the immersion electrical property of product.Prior art is from document On be difficult to find, but typically use high-quality plasticizer, reduce or without the mode of filler, product index performance is still difficult to meet The problems such as requirement, easily causes the indexs such as thermal deformation defective simultaneously, cost increase.
Summary of the invention
First purpose of the present invention is to provide a kind of waterproof flame retardant restrictive coating on cable, and it greatly reduces electricity The water absorption of cable restrictive coating, product uses under moist or water-immerged environment, further increases electric property stable, does not produces Changing, improves the compactness of product, gets rid of material micropore.
Second object of the present invention is to provide a kind of manufacture preparing above-mentioned waterproof flame retardant restrictive coating on cable Technique.
For reaching above-mentioned first goal of the invention, the technical solution used in the present invention is: a kind of waterproof flame retardant for cable Restrictive coating, described cable includes cable core and is coated on the waterproof flame retardant restrictive coating of cable core outer surface, described waterproof flame retardant restrictive coating It is made up of the component of following weight portion:
Polrvinyl chloride 100 parts,
Trioctyl trimellitate (TOTM) (TOTM) 20 ~ 30 parts,
Diisooctyl phthalate 15 ~ 25 parts,
Environmental protection calcium-zinc composite stabilizing agent 5 ~ 10 parts,
Compound rare-earth stabilizer 5 ~ 10 parts,
Antimony oxide 4 ~ 8 parts,
Lubricant 0.3 ~ 1 part,
0.1 ~ 0.5 part of antioxidant,
Nano barium sulfate 3.5 ~ 7 parts,
Calcined kaolin 2.6 ~ 5.2 parts,
Nano silicon 3.5 ~ 7 parts,
Silane coupler 0.18 ~ 0.36 part.
The technical scheme improved further in above-mentioned waterproof flame retardant restrictive coating technical scheme is as follows:
1, in such scheme, described silane coupler is vinyl three ('beta '-methoxy ethyoxyl) silane, vinyl front three TMOS or γ-glycidyl ether oxygen propyl trimethoxy silicane.
2, in such scheme, described silane coupler is vinyl three ('beta '-methoxy ethyoxyl) silane, vinyl front three TMOS and γ-glycidyl ether oxygen propyl trimethoxy silicane press the mixing of 10:5:3 weight ratio.
3, in such scheme, described lubricant is Tissuemat E or stearic acid.
4, in such scheme, described antioxidant [3-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] tetramethylolmethane that is four Ester or bisphenol-A.
5, in such scheme, described calcined kaolin adds the improver of gross weight 1.5 ~ 2%, calcination when in calcination Temperature 970 ~ 990 DEG C, the time is 30 ~ 40 minutes;Described improver is made up of cleaned coal, sodium sulfate and sodium chloride, this cleaned coal, sulfur Acid sodium and sodium chloride press the mixing of 10:0. 5:0. 3 weight.
For reaching above-mentioned second goal of the invention, the technical solution used in the present invention is: a kind of waterproof flame retardant for cable The manufacturing process of restrictive coating, comprises the following steps:
Comprise the following steps:
Step one, polrvinyl chloride 100 parts is mixed to form mixture through high-speed mixer under high-speed stirred state;Start Stirring at low speed, rotating speed 500rpm, add trioctyl trimellitate (TOTM) 20 ~ 30 parts and diisooctyl phthalate 15 ~ 25 parts, start High-speed stirred, rotating speed 1000rpm, treating material temperature to rise to 80 DEG C, to add environmental protection calcium-zinc composite stabilizing agents 5 ~ 10 parts, compound rare-earth stable Agent 5 ~ 10 parts, antimony oxide 4 ~ 8 parts, lubricant 0.3 ~ 1 part, 0.1 ~ 0.5 part of antioxidant and water-proofing agent 10 ~ 20 parts, continue to stir Mix to 110 DEG C of materials of temperature in dry powdered form, open baiting valve blowing;
Step 2, the compound of step one is put that to carry out extrusion molding to twin screw mixing, make subsequently into single multiple screw extruder Grain, uses the fervent prilling of die face, the particle made by blower fan conveyance conduit enter first order whirlwind cooling separator, the Two grades of whirlwind cooling separators, air-cooled vibrosieve, third level whirlwind cooling separators obtain described waterproof flame retardant PVC cable material;
Described water-proofing agent obtains through following technique:
Step one, by described nano barium sulfate 3.5 ~ 7 parts, calcined kaolin 2.6 ~ 5.2 parts, nano silicon 3.5 ~ 7 Part carries out Surface coating process;
Step 2, the powder of said components being put in high-speed mixer, mixed at high speed takes off to temperature 90 ~ 100 DEG C Water 3 ~ 5min;
Step 3, powder is carried out at cladding by silane coupler 0.18 ~ 0.36 part in vaporific spraying in high-speed mixer Reason, continues mixed at high speed and carries out material surface cladding process reaction 3 ~ 5min;
Described water-proofing agent is obtained after step 4, cooling.
The technical scheme improved further in technique scheme is as follows:
In such scheme, described calcined kaolin adds the improver of gross weight 1.5 ~ 2%, calcination temperature when in calcination Spending 970 ~ 990 DEG C, the time is 30 ~ 40 minutes;Described improver is made up of cleaned coal, sodium sulfate and sodium chloride, this cleaned coal, sulphuric acid Sodium and sodium chloride press the mixing of 10:0. 5:0. 3 weight.
Due to the utilization of technique scheme, the present invention compared with prior art has the advantage that
The present invention is used for the waterproof flame retardant restrictive coating on cable and manufacturing process thereof, which overcomes the increasing of existing product formula Mould agent and water absorption that filler all has, thus the most easily occur that properties of product decline the technological deficiency of phenomenon, The present invention consider all of formula materials all with the problem of the compatibility of water, select specific hydrophobic material and content.To powder Carry out Surface coating process after predrainage, improve the hydrophobic performance of product;Product uses under moist or water-immerged environment, electrical resistance Can be stable, the most do not produce change;Water-proofing agent material selection nanoscale raw material, improves the compactness of product, gets rid of material micropore, Steam cannot invade and cause hydraulic performance decline.
Accompanying drawing explanation
Fig. 1 is the construction of cable schematic diagram that the present invention has waterproof flame retardant restrictive coating.
In the figures above: 1, cable core;2, waterproof flame retardant restrictive coating.
Detailed description of the invention
Below in conjunction with the accompanying drawings and embodiment the invention will be further described:
Embodiment 1: a kind of waterproof flame retardant restrictive coating on cable, described cable includes cable core 1 and is coated on cable core 1 The waterproof flame retardant restrictive coating 2 of outer surface, described waterproof flame retardant restrictive coating 2 is made up of the component of following weight portion, as shown in table 1:
Table 1
More than it is weight portion.
Above-mentioned silane coupler be vinyl three ('beta '-methoxy ethyoxyl) silane, vinyltrimethoxy silane or γ-glycidyl ether oxygen propyl trimethoxy silicane.
Above-mentioned silane coupler be vinyl three ('beta '-methoxy ethyoxyl) silane, vinyltrimethoxy silane and γ- Glycidyl ether oxygen propyl trimethoxy silicane presses the mixing of 10:5:3 weight ratio.
Above-mentioned lubricant embodiment 1 is Tissuemat E, and lubricant embodiment 2 is stearic acid, and lubricant embodiment 3 is poly-second Alkene wax and stearic complex.
Above-mentioned antioxidant embodiment 1 [3-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester that is four, implements Example 2 is bisphenol-A, embodiment 3 [3-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester that is four.
Above-mentioned calcined kaolin is the improver of addition gross weight 1.5 ~ 2% when in calcination, calcination temperature 970 ~ 990 DEG C, Time is 30 ~ 40 minutes;Described improver is made up of cleaned coal, sodium sulfate and sodium chloride, and this cleaned coal, sodium sulfate and sodium chloride are pressed 10:0. 5:0. 3 weight mixes.
The preparation technology of above-mentioned waterproof flame retardant PVC cable material, comprises the following steps:
Step one, by the degree of polymerization be 590~720 polrvinyl chloride 55 ~ 65 parts, the degree of polymerization be that 1110~1340 polrvinyl chloride are 35 ~ 45 parts are mixed to form mixture through high-speed mixer under high-speed stirred state;Start stirring at low speed, rotating speed 500rpm, add Enter trioctyl trimellitate (TOTM) 20 ~ 30 parts and diisooctyl phthalate 15 ~ 25 parts, start high-speed stirred, rotating speed 1000rpm, Treat that material temperature rises to 80 DEG C and adds environmental protection calcium-zinc composite stabilizing agent 5 ~ 10 parts, compound rare-earth stabilizer 5 ~ 10 parts, antimony oxide 4 ~ 8 Part, lubricant 0.3 ~ 1 part, 0.1 ~ 0.5 part of antioxidant and water-proofing agent 10 ~ 20 parts, continuation stirring are dry powder to 110 DEG C of materials of temperature Shape, opens baiting valve blowing;
Step 2, the compound of step one is put that to carry out extrusion molding to twin screw mixing, make subsequently into single multiple screw extruder Grain, uses the fervent prilling of die face, the particle made by blower fan conveyance conduit enter first order whirlwind cooling separator, the Two grades of whirlwind cooling separators, air-cooled vibrosieve, third level whirlwind cooling separators obtain described waterproof flame retardant PVC cable material;
Described water-proofing agent obtains through following technique:
Step one, by described nano barium sulfate 3.5 ~ 7 parts, calcined kaolin 2.6 ~ 5.2 parts, nano silicon 3.5 ~ 7 Part carries out Surface coating process;
Step 2, the powder of said components being put in high-speed mixer, mixed at high speed takes off to temperature 90 ~ 100 DEG C Water 3 ~ 5min;
Step 3, powder is carried out at cladding by silane coupler 0.18 ~ 0.36 part in vaporific spraying in high-speed mixer Reason, continues mixed at high speed and carries out material surface cladding process reaction 3 ~ 5min;
Described water-proofing agent is obtained after step 4, cooling.
Above-mentioned calcined kaolin is the improver of addition gross weight 1.5 ~ 2% when in calcination, calcination temperature 970 ~ 990 DEG C, Time is 30 ~ 40 minutes;Described improver is made up of cleaned coal, sodium sulfate and sodium chloride, and this cleaned coal, sodium sulfate and sodium chloride are pressed 10:0. 5:0. 3 weight mixes.
Manufacturing process is with embodiment 1.
Water resistance test uses " ASTM D2219-02 electric wire and cable pvc material specification " 5.5 tests Condition (electric current 60Hz frequency, temperature of soaking: 50 ± 1 DEG C).
Test result analysis: the accelerated water absorption test of product, change in dielectric constant rate much smaller than standard (1 ~ 14d, 10%;7~ 14d, 5%) requirement, product has good water resistance.
To sum up, waterproof flame retardant restrictive coating of the present invention and manufacturing process thereof, which overcome existing product formula plasticizer and The water absorption that filler all has, thus the most easily occur that properties of product decline the technological deficiency of phenomenon;The present invention Consider all of formula materials all with the compatibility of water, select hydrophobic material.Carry out at Surface coating after powder predrainage Reason, improves the hydrophobic performance of product;Product uses under moist or water-immerged environment, and electric property is stable, does not the most produce change; Water-proofing agent material selection nanoscale raw material, improves the compactness of product, gets rid of material micropore, and steam cannot invade and cause under performance Fall.
Above-described embodiment, only for technology design and the feature of the explanation present invention, its object is to allow person skilled in the art Scholar will appreciate that present disclosure and implements according to this, can not limit the scope of the invention with this.All according to the present invention The equivalence that spirit is made changes or modifies, and all should contain within protection scope of the present invention.

Claims (8)

1., for a waterproof flame retardant restrictive coating for cable, described cable includes cable core (1) and is coated on cable core (1) outer surface Waterproof flame retardant restrictive coating (2), it is characterised in that: described waterproof flame retardant restrictive coating (2) is made up of the component of following weight portion:
Polrvinyl chloride 100 parts,
Trioctyl trimellitate (TOTM) (TOTM) 20 ~ 30 parts,
Diisooctyl phthalate 15 ~ 25 parts,
Environmental protection calcium-zinc composite stabilizing agent 5 ~ 10 parts,
Compound rare-earth stabilizer 5 ~ 10 parts,
Antimony oxide 4 ~ 8 parts,
Lubricant 0.3 ~ 1 part,
0.1 ~ 0.5 part of antioxidant,
Nano barium sulfate 3.5 ~ 7 parts,
Calcined kaolin 2.6 ~ 5.2 parts,
Nano silicon 3.5 ~ 7 parts,
Silane coupler 0.18 ~ 0.36 part;
Wherein, described nano barium sulfate, calcined kaolin, nano silicon and silane coupler are formed by following technique Water-proofing agent:
Step one, described nano barium sulfate 3.5 ~ 7 parts, calcined kaolin 2.6 ~ 5.2 parts, nano silicon 3.5 ~ 7 parts are entered Row Surface coating processes;
Step 2, the powder of said components is put in high-speed mixer, mixed at high speed to temperature 90 ~ 100 DEG C carries out being dehydrated 3 ~ 5min;
Step 3, silane coupler 0.18 ~ 0.36 part is carried out cladding process in vaporific spraying in high-speed mixer to powder, continue Continuous mixed at high speed carries out material surface cladding and processes reaction 3 ~ 5min;
Described water-proofing agent is obtained after step 4, cooling.
Waterproof flame retardant restrictive coating the most according to claim 1, it is characterised in that: described silane coupler is vinyl three ('beta '-methoxy ethyoxyl) silane, vinyltrimethoxy silane or γ-glycidyl ether oxygen propyl trimethoxy silicane.
Waterproof flame retardant restrictive coating the most according to claim 1, it is characterised in that: described silane coupler is vinyl three ('beta '-methoxy ethyoxyl) silane, vinyltrimethoxy silane and γ-glycidyl ether oxygen propyl trimethoxy silicane are by 10: 5:3 weight ratio mixes.
Waterproof flame retardant restrictive coating the most according to claim 1, it is characterised in that: described lubricant is Tissuemat E or hard Fat acid.
Waterproof flame retardant restrictive coating the most according to claim 1, it is characterised in that: described antioxidant [3-(3,5-bis-uncle that is four Butyl-4-hydroxy phenyl) propanoic acid] pentaerythritol ester or bisphenol-A.
Waterproof flame retardant restrictive coating the most according to claim 1, it is characterised in that: described calcined kaolin is when in calcination Adding the improver of gross weight 1.5 ~ 2%, calcination temperature 970 ~ 990 DEG C, the time is 30 ~ 40 minutes;Described improver is by essence Coal, sodium sulfate and sodium chloride composition, this cleaned coal, sodium sulfate and sodium chloride press the mixing of 10:0. 5:0. 3 weight.
7. the manufacturing process of waterproof flame retardant restrictive coating as claimed in claim 1, it is characterised in that: comprise the following steps:
Step one, polrvinyl chloride 100 parts is mixed to form mixture through high-speed mixer under high-speed stirred state;Start low speed Stirring, rotating speed 500rpm, add trioctyl trimellitate (TOTM) 20 ~ 30 parts and diisooctyl phthalate 15 ~ 25 parts, start at a high speed Stirring, rotating speed 1000rpm, treat material temperature rise to 80 DEG C add environmental protection calcium-zinc composite stabilizing agents 5 ~ 10 parts, compound rare-earth stabilizer 5 ~ 10 parts, antimony oxide 4 ~ 8 parts, lubricant 0.3 ~ 1 part, 0.1 ~ 0.5 part of antioxidant and water-proofing agent 10 ~ 20 parts, continuation stirring are extremely 110 DEG C of materials of temperature are in dry powdered form, open baiting valve blowing;
Step 2, the compound of step one is put that to carry out extrusion molding to twin screw mixing, subsequently into single multiple screw extruder pelletize, adopt By the fervent prilling of die face, the particle made enters first order whirlwind cooling separator, the second level by blower fan conveyance conduit Whirlwind cooling separator, air-cooled vibrosieve, third level whirlwind cooling separator obtain described waterproof flame retardant PVC cable material;
Described water-proofing agent obtains through following technique:
Step one, described nano barium sulfate 3.5 ~ 7 parts, calcined kaolin 2.6 ~ 5.2 parts, nano silicon 3.5 ~ 7 parts are entered Row Surface coating processes;
Step 2, the powder of said components is put in high-speed mixer, mixed at high speed to temperature 90 ~ 100 DEG C carries out being dehydrated 3 ~ 5min;
Step 3, silane coupler 0.18 ~ 0.36 part is carried out cladding process in vaporific spraying in high-speed mixer to powder, continue Continuous mixed at high speed carries out material surface cladding and processes reaction 3 ~ 5min;
Described water-proofing agent is obtained after step 4, cooling.
Manufacturing process the most according to claim 7, it is characterised in that: described calcined kaolin adds total when in calcination The improver of weight 1.5 ~ 2%, calcination temperature 970 ~ 990 DEG C, the time is 30 ~ 40 minutes;Described improver is by cleaned coal, sulphuric acid Sodium and sodium chloride composition, this cleaned coal, sodium sulfate and sodium chloride press the mixing of 10:0. 5:0. 3 weight.
CN201210512702.9A 2012-12-04 2012-12-04 Waterproof flame retardant restrictive coating and manufacturing process thereof for cable Active CN103849084B (en)

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CN201210512702.9A CN103849084B (en) 2012-12-04 2012-12-04 Waterproof flame retardant restrictive coating and manufacturing process thereof for cable

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CN201610426627.2A CN106221053A (en) 2012-12-04 2012-12-04 There is the PVC fire proofing of hydrophobic performance
CN201210512702.9A CN103849084B (en) 2012-12-04 2012-12-04 Waterproof flame retardant restrictive coating and manufacturing process thereof for cable
CN201610425093.1A CN105949662A (en) 2012-12-04 2012-12-04 Flame-retardant jacket material for low-medium voltage cable

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CN201610425093.1A Division CN105949662A (en) 2012-12-04 2012-12-04 Flame-retardant jacket material for low-medium voltage cable
CN201610426627.2A Division CN106221053A (en) 2012-12-04 2012-12-04 There is the PVC fire proofing of hydrophobic performance

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CN103849084A CN103849084A (en) 2014-06-11
CN103849084B true CN103849084B (en) 2016-08-10

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CN201610425093.1A Pending CN105949662A (en) 2012-12-04 2012-12-04 Flame-retardant jacket material for low-medium voltage cable
CN201610426627.2A Pending CN106221053A (en) 2012-12-04 2012-12-04 There is the PVC fire proofing of hydrophobic performance
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CN104356542A (en) * 2014-10-30 2015-02-18 安徽电信器材贸易工业有限责任公司 Flame-retardant PVC (polyvinyl chloride) sheath material for ultrahigh-voltage cables and preparation method of material
CN104371216A (en) * 2014-10-30 2015-02-25 安徽电信器材贸易工业有限责任公司 Water-resistant polyvinyl chloride cable sheath material and preparation method thereof
CN109096653A (en) * 2018-08-21 2018-12-28 山东寰宇线缆有限公司 A kind of applicable high-speed production automobile polyvinyl chloride cable material and preparation method thereof
CN109265861A (en) * 2018-08-31 2019-01-25 安庆市泽烨新材料技术推广服务有限公司 Network system cable sheath material and preparation method thereof
CN109776999A (en) * 2018-12-29 2019-05-21 安徽天康(集团)股份有限公司 A kind of high temperature resistance control cable

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