CN106009227A - Halogen-free low-smoke flame-retardant oxygen insulation layer insulating material and preparation method thereof - Google Patents

Halogen-free low-smoke flame-retardant oxygen insulation layer insulating material and preparation method thereof Download PDF

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CN106009227A
CN106009227A CN201610545974.7A CN201610545974A CN106009227A CN 106009227 A CN106009227 A CN 106009227A CN 201610545974 A CN201610545974 A CN 201610545974A CN 106009227 A CN106009227 A CN 106009227A
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prepared
silane
insulant
catalyst masterbatch
lldpe
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赵勇
俞丽琴
蔡煜明
李顺利
郑颜
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Long-Range New Material Ltd Co Of Zhejiang Taihu
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Long-Range New Material Ltd Co Of Zhejiang Taihu
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    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/08Copolymers of ethene
    • C08L23/0807Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815Copolymers of ethene with aliphatic 1-olefins
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00Making granules
    • B29B9/02Making granules by dividing preformed material
    • B29B9/06Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
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    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/20Compounding polymers with additives, e.g. colouring
    • C08J3/22Compounding polymers with additives, e.g. colouring using masterbatch techniques
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    • C08J2323/00Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04Homopolymers or copolymers of ethene
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    • C08J2423/00Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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    • C08J2423/00Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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    • C08L2201/00Properties
    • C08L2201/02Flame or fire retardant/resistant
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    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/08Stabilised against heat, light or radiation or oxydation
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    • C08L2201/00Properties
    • C08L2201/22Halogen free composition
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    • C08L2203/00Applications
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    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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    • C08L2207/00Properties characterising the ingredient of the composition
    • C08L2207/06Properties of polyethylene
    • C08L2207/066LDPE (radical process)
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    • C08L2312/00Crosslinking
    • C08L2312/08Crosslinking by silane
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00Insulated conductors or cables characterised by their form
    • H01B7/02Disposition of insulation
    • H01B7/0275Disposition of insulation comprising one or more extruded layers of insulation
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00Insulated conductors or cables characterised by their form
    • H01B7/17Protection against damage caused by external factors, e.g. sheaths or armouring
    • H01B7/29Protection against damage caused by extremes of temperature or by flame
    • H01B7/295Protection against damage caused by extremes of temperature or by flame using material resistant to flame

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Abstract

The invention relates to the field of insulating materials, in particular to a halogen-free low-smoke flame-retardant oxygen insulation layer insulating material and a preparation method thereof. The insulating material is prepared from, by weight, LLDPE-7042, LLDPE-8320, LDPE, EVA, PP, a silane coupling agent, a cross-linking agent DCP, an antioxidant 300, an antioxidant 1010, an antioxidant DLTP, an antioxidant 1024, organotin and magnesium hydroxide or aluminum hydroxide. The insulating material is mainly used for insulating layers of cables and mainly replaces a current PVC material, the insulating property is superior to that of PVC, PVC can emit toxic and harmful gases when the wires fire due to aging and the like, and the silane insulating material is poisonless and harmless.

Description

LSOH anti-flaming oxygen barrier layer insulant and preparation method thereof
Technical field
The present invention relates to insulant field, particularly relate to LSOH anti-flaming oxygen barrier layer insulant and preparation method thereof.
Background technology
Cable industry uses polyolefinic kind mainly to have PE, PP, EVA and EEA etc., and wherein relative quantity is big, applicating history is long Mainly PE, it has HDPE, MDPE, LDPE, LLDPE and the XLPE through crosslinking, and their application does not the most need to speak more. In industry, the most polyolefinic application and development trend are concentrated mainly on following several respects:
(1) seriation of low smoke, zero halogen material, improvement
Halide-free low-smoke fireproof cable material is development in recent years kind faster, has met the thermoplastic moulding mixture of IEC92-359 standard-required Increasingly it is widely applied.Use occasion along with oil platform, nuclear power station, cable for ship and other bad environments Requirement, the range of application of cross-linking type low smoke, zero halogen CABLE MATERIALS will be increasing.
(2) resistance to electricity trace material
Resistance to electricity trace CABLE MATERIALS is as the popularization and application of ADSS (All Dielectric Self-Supporting Aerial Optical Fiber Cable), and gradually causes everybody note Meaning.In fact, the trace requirement of resistance to electricity is had for producing corona under preventing at damp condition, due to it at 10kV and above aerial cable Insulant (XLPE, HDPE) itself has certain resistance to electricity trace, substantially can guarantee that the requirement of aerial cable resistance to electricity trace, therefore And problem does not highlight.And ADSS mainly sets up along the high-tension line of 110KV, 220KV, the electric erosion resistance of its sheath will Directly affect cable lifetime, therefore the resistance to electricity trace of sheath material is had more harsh requirement, i.e. apply actually used pulling force In the case of 90% tension force, carrying out the resistance to electricity trace test of 1000 hours, it needs this custom-designed formula system promising, therein Key is resistance to the electricity use of trace agent, superior physical and mechanical properties, the balance of good process processability.At present, English, moral, The life search of ADSS is also being continued by Mei Deng state, and the most how its emphasis improves is placed in the anti-of cable sheath material in space electric field Galvanic corrosion.
(3) crosslinked with silicane material
Organosilane crosslinked polyethylene insulation material commonly uses in 3KV and following power cable.Along with popularizing of crosslinked with silicane technology, Other has product to come out such as crosslinked with silicane strippable shielding material, LSOH anti-flaming material, second the third CABLE MATERIALS the most in succession.Domestic at silicon On alkane crosslinking strippable shielding material, existing producer works, and silane crosslinked halogen-free flame-retardant material, second the third CABLE MATERIALS are still few for everybody Understand, certainly let alone apply.
(4) cross-linking radiation polyolefin material
Cross-linking radiation material and technology have obtained the application of maturation on power cable, aerial cable and equipment line.It is known that 105 DEG C and temperature below grade in industry, all can meet requirement with XLPE, XLPVC or PVC, more than 150 DEG C, silicon rubber The application of the kinds such as glue, fluoroplastics, polyimides is the most ripe, but answering in medium temperature grade (such as 125 DEG C, 150 DEG C) With in exploitation, bigger with external gap.
Summary of the invention
In order to solve above-mentioned technical problem, it is an object of the invention to provide LSOH anti-flaming oxygen barrier layer insulant.This material Being mainly used in the insulating barrier of cable, to replace current PVC material, insulating properties are better than PVC, and PVC is old at electric wire Changes etc. can release toxic and harmful when on fire, and silane Insulation Material is nontoxic.
In order to realize above-mentioned purpose, present invention employs following technical scheme:
LSOH anti-flaming oxygen barrier layer insulant, this insulant is prepared by following component by weight percentage:
Described catalyst masterbatch is prepared by following component:
As preferably, this insulant is prepared by following component by weight percentage:
Described catalyst masterbatch is prepared by following component:
Two step method prepares the method for LSOH anti-flaming oxygen barrier layer insulant, and the method comprises the following steps:
1) prepared by catalyst masterbatch: stirred in blender by the material of above catalyst masterbatch, and first stirring at low speed 1 minute is the highest Speed stirring 3 minutes, then releases and pours extruder hopper into, and extruder temperature: 140~180 DEG C, through supercool after twin-screw extrusion But tank cools down, then carries out pelletizing after blower fan dries up, and granule, at drying tower, arranges 80 DEG C and dries more than 2 hours so Carry out packing, temporarily depositing with vacuum aluminium plastic bag afterwards;
2) prepared by finished product:
2.1) silane coupler, crosslink agent DCP, antioxidant 300 are proportionally mixed, after mixing, become silane adjuvant, It is sufficiently mixed rear silane adjuvant stand-by;
2.2) LLDPE-7042, LLDPE-8320, LDPE, EVA, catalysis masterbatch are drawn into blender in proportion and mix, Sucking drying tower after mix homogeneously, set 60 DEG C, drying time is more than half an hour, and material sucks raw material feed bin afterwards;
2.3) above material joins double screw extruder through weighing balance auto feed, and the silane adjuvant prepared is also passed through meter Amount claims to join twin screw in the secondth district, and above material is grafted at twin screw;
2.4) material after twin screw is grafted is through Single screw extrusion, eccentric water smoke pelletizing, is transported to dewaterer through transportation water pump, Through dehydration after be delivered to ebullated bed by conveying fan, by control material position height material is fully dried, after inhaled by vacuum Material machine sucks finished product bin;
2.5) measure, pack and be finished product.
The method of the LSOH anti-flaming oxygen barrier layer insulant described in one-step method preparation, the method comprises the following steps:
1) prepared by catalyst masterbatch: stirred in blender by the material of above catalyst masterbatch, and first stirring at low speed 1 minute is the highest Speed stirring 3 minutes, then releases and pours extruder hopper into, and extruder temperature: 140~180 DEG C, through supercool after twin-screw extrusion But tank cools down, then carries out pelletizing after blower fan dries up, and granule, at drying tower, arranges 80 DEG C and dries more than 2 hours so Carry out packing, temporarily depositing with vacuum aluminium plastic bag afterwards;
2) prepared by finished product:
2.1) silane coupler, crosslink agent DCP, antioxidant 300 are proportionally mixed, after mixing, become silane adjuvant, It is sufficiently mixed rear silane adjuvant stand-by;
2.2) carry out being heated to 90 DEG C by main equipment double conical rotary vessel;
2.3) LLDPE-7042, LLDPE-8320, LDPE, EVA, catalysis masterbatch are drawn in double conical rotary vessel, then in proportion Lid is airtight, open double conical rotary vessel and be dried, mix;
2.4) above dry materials, mixing 2.5 hours after, by liquid spraying device, standby silane adjuvant is joined material In;
2.5) silane adjuvant is released after the absorption of 2.5 hours;
2.6) measure, pack and be finished product.
Due to the fact that and have employed above-mentioned technical scheme, the material of the present invention is mainly used in the insulating barrier of cable, to replace at present PVC material be main, insulating properties are better than PVC, and PVC electric wire aging etc. on fire when can release toxic and harmful, And silane Insulation Material is nontoxic.
Use the production of the present invention, screw speed and current stabilization, produce 240mm2, 4.5 meters per minute of payingoff speed; When extrusion, plastic emitting is uniform, and without granule, start occurs for 12 days without old glue continuously;The extension of cable heat detects 70%~80%, Permanent deformation is in the range of 0~5%;Partial Discharge Detection is within 2PC, and industrial frequency withstand voltage tests 30 minutes without puncturing;Semi-finished product, Finished product detection all meets GB/T 12706-2002 requirement.
The product of the present invention compares with polrvinyl chloride, and thermal denaturation resistant is better than PvC, and anti-overload ability is strong.Short circuit operation temperature is the highest Up to 250 DEG C.And PVC poor heat resistance, its 80 DEG C continue its degeneration of 4h up to 50%.When cable overlond running easy Causing insulation ag(e)ing and soften degeneration and cause and puncture, PVC is aging causes Cable Firing Accident to account for the 50% of electricity fire incident sum; Crosslinked polyethylene density is less by about 40% than polrvinyl chloride, can substantially alleviate the quality of cable.Compare with thermoplastic polyethylene, Improve resistance to heat distorsion, improve the mechanical property under high temperature, improve environmental stress resistance be full of cracks and heat aging property, increase Strong chemical-resistant stability and solvent resistance, decrease cold flow properties, and insulation resistance is high, and dielectric loss angle tangent is little, the most not Change with the change of temperature, substantially maintain original electric property.
Detailed description of the invention
Embodiment 1
LSOH anti-flaming oxygen barrier layer insulant, this insulant is prepared by following component by weight percentage:
Two step method prepares the method for LSOH anti-flaming oxygen barrier layer insulant, is mainly made up of two parts, and one is catalyst masterbatch Preparation, two is prepared by finished product.
1, prepared by catalyst masterbatch: catalyst masterbatch accounts for the 5% of total material composition, and concrete formula is as follows:
Above material is stirred in blender, first stirring at low speed 1 minute high-speed stirred 3 minutes again, then release and pour extrusion into Machine hopper (extruder temperature: 140~180 DEG C), cools down through supercooling tank after twin-screw extrusion, then blows through blower fan Carrying out pelletizing after Gan, granule is dried at drying tower (arranging 80 DEG C) and then is carried out packing, temporarily with vacuum aluminium plastic bag for more than 2 hours Shi Cunfang.
2, prepared by finished product:
2.1) silane coupler, cross-linking agent, antioxidant 300 are carried out mixing (mixed according to the ratio of 1.6%:0.13%:0.04% Silane adjuvant is become after conjunction), it is sufficiently mixed rear silane adjuvant stand-by;
2.2) by LLDPE-7042, LLDPE-8320, LDPE, EVA, catalysis masterbatch according to 40%:20%:25%:8.23%: The ratio of 5% is drawn into blender and mixes, and sucks drying tower, set 60 DEG C after mix homogeneously, and drying time is more than little half Time, afterwards material is sucked raw material feed bin;
2.3) above material joins double screw extruder through weighing balance auto feed, and the silane adjuvant prepared is also passed through meter Amount claims to join twin screw in the secondth district, and above material is grafted at twin screw;
2.4) material after twin screw is grafted is through Single screw extrusion, eccentric water smoke pelletizing, is transported to dewaterer through transportation water pump, Through dehydration after be delivered to ebullated bed by conveying fan, by control material position height material is fully dried, after inhaled by vacuum Material machine sucks finished product bin;
2.4) measure, pack and be finished product.
2.5) detecting product prepared as above, testing result is qualified.
Embodiment 2
LSOH anti-flaming oxygen barrier layer insulant, this insulant is prepared by following component by weight percentage:
Above-mentioned insulant uses the two step method of embodiment 1 to prepare insulant.
Embodiment 3
LSOH anti-flaming oxygen barrier layer insulant, this insulant is prepared by following component by weight percentage:
One-step method prepares the method for LSOH anti-flaming oxygen barrier layer insulant.Mainly being made up of two parts, one is catalyst masterbatch Preparation, two is prepared by finished product.
One, prepared by catalyst masterbatch: catalyst masterbatch accounts for the 5% of total material composition, and concrete formula is as follows:
Above material is stirred in blender, first stirring at low speed 1 minute high-speed stirred 3 minutes again, then release and pour extrusion into Machine hopper (extruder temperature: 140~180 DEG C), cools down through supercooling tank after twin-screw extrusion, then blows through blower fan Carrying out pelletizing after Gan, granule is dried at drying tower (arranging 80 DEG C) and then is carried out packing, temporarily with vacuum aluminium plastic bag for more than 2 hours Shi Cunfang.
Two, prepared by finished product:
1, silane coupler, cross-linking agent, antioxidant 300 are carried out mixing (mixed according to the ratio of 1.6%:0.13%:0.04% Silane adjuvant is become after conjunction), it is sufficiently mixed rear silane adjuvant stand-by;
2, carry out being heated to 90 DEG C by main equipment double conical rotary vessel;
3, by LLDPE-7042, LLDPE-8320, LDPE, EVA, catalysis masterbatch according to 40%:20%:25%:8.23%:5% Ratio be drawn in double conical rotary vessel, then that lid is airtight, open double conical rotary vessel be dried, mix;
4, above dry materials, mixing 2.5 hours after, by liquid spraying device, standby silane adjuvant is joined in material;
5, silane adjuvant is released after the absorption of 2.5 hours;
6, measure, pack and be finished product.
7, detecting product prepared as above, testing result is qualified.
Embodiment 4
LSOH anti-flaming oxygen barrier layer insulant, this insulant is prepared by following component by weight percentage:
Above-mentioned insulant uses the one-step method of embodiment 3 to prepare insulant.

Claims (4)

1. LSOH anti-flaming oxygen barrier layer insulant, it is characterised in that this insulant is by weight percentage by following component system For obtaining:
And catalyst masterbatch;
Described catalyst masterbatch is prepared by following component:
LSOH anti-flaming oxygen barrier layer insulant the most according to claim 1, it is characterised in that this insulant by weight hundred Proportion by subtraction meter is prepared by following component:
And catalyst masterbatch;
Described catalyst masterbatch is prepared by following component:
3. the method that two step method prepares the LSOH anti-flaming oxygen barrier layer insulant described in claim 1 or 2, it is characterised in that should Method comprises the following steps:
1) prepared by catalyst masterbatch: stirred in blender by the material of above catalyst masterbatch, and first stirring at low speed 1 minute is the highest Speed stirring 3 minutes, then releases and pours extruder hopper into, and extruder temperature: 140~180 DEG C, through supercool after twin-screw extrusion But tank cools down, then carries out pelletizing after blower fan dries up, and granule, at drying tower, arranges 80 DEG C and dries more than 2 hours so Carry out packing, temporarily depositing with vacuum aluminium plastic bag afterwards;
2) prepared by finished product:
2.1) silane coupler, crosslink agent DCP, antioxidant 300 are proportionally mixed, become silane after mixing and help Agent, is sufficiently mixed rear silane adjuvant stand-by;
2.2) LLDPE-7042, LLDPE-8320, LDPE, EVA, catalysis masterbatch are drawn into blender in proportion and mix Closing, suck drying tower, set 60 DEG C after mix homogeneously, drying time is more than half an hour, and material sucks raw material feed bin afterwards;
2.3) above material joins double screw extruder through weighing balance auto feed, and the silane adjuvant prepared is also passed through meter Amount claims to join twin screw in the secondth district, and above material is grafted at twin screw;
2.4) material after twin screw is grafted is through Single screw extrusion, eccentric water smoke pelletizing, is transported to dewaterer through transportation water pump, Through dehydration after be delivered to ebullated bed by conveying fan, by control material position height material is fully dried, after inhaled by vacuum Material machine sucks finished product bin;
2.5) measure, pack and be finished product.
4. the method that one-step method prepares the LSOH anti-flaming oxygen barrier layer insulant described in claim 1 or 2, the method include with Under step:
1) prepared by catalyst masterbatch: stirred in blender by the material of above catalyst masterbatch, and first stirring at low speed 1 minute is the highest Speed stirring 3 minutes, then releases and pours extruder hopper into, and extruder temperature: 140~180 DEG C, through supercool after twin-screw extrusion But tank cools down, then carries out pelletizing after blower fan dries up, and granule, at drying tower, arranges 80 DEG C and dries more than 2 hours so Carry out packing, temporarily depositing with vacuum aluminium plastic bag afterwards;
2) prepared by finished product:
2.1) silane coupler, crosslink agent DCP, antioxidant 300 are proportionally mixed, after mixing, become silane adjuvant, It is sufficiently mixed rear silane adjuvant stand-by;
2.2) carry out being heated to 90 DEG C by main equipment double conical rotary vessel;
2.3) LLDPE-7042, LLDPE-8320, LDPE, EVA, catalysis masterbatch are drawn in double conical rotary vessel, so in proportion After lid is airtight, open double conical rotary vessel be dried, mix;
2.4) above dry materials, mixing 2.5 hours after, by liquid spraying device, standby silane adjuvant is joined material In;
2.5) silane adjuvant is released after the absorption of 2.5 hours;
2.6) measure, pack and be finished product.
CN201610545974.7A 2016-07-08 2016-07-08 Halogen-free low-smoke flame-retardant oxygen insulation layer insulating material and preparation method thereof Pending CN106009227A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101585214A (en) * 2009-06-18 2009-11-25 上海交通大学 Method for preparing crosslinkable polyethylene cable material
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CN102443212A (en) * 2011-09-16 2012-05-09 无锡丰力弹簧有限公司 Special material for quick organosilane crosslinked polyethylene and preparation method of special material
CN102746548A (en) * 2012-06-04 2012-10-24 安徽扬天塑业科技有限公司 Water distillation-free rapid silane natural crosslinking polyethylene cable material and preparation method thereof
CN104177695A (en) * 2014-09-17 2014-12-03 朱忠良 Crosslinked halogen-free flame-retardant cable material

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Publication number Priority date Publication date Assignee Title
CN101585214A (en) * 2009-06-18 2009-11-25 上海交通大学 Method for preparing crosslinkable polyethylene cable material
CN102443212A (en) * 2011-09-16 2012-05-09 无锡丰力弹簧有限公司 Special material for quick organosilane crosslinked polyethylene and preparation method of special material
CN102321295A (en) * 2011-09-29 2012-01-18 广州凯恒科塑有限公司 Low smoke zero halogen flame-retardant mould shrinkage sleeve and preparation method as well as application thereof
CN102746548A (en) * 2012-06-04 2012-10-24 安徽扬天塑业科技有限公司 Water distillation-free rapid silane natural crosslinking polyethylene cable material and preparation method thereof
CN104177695A (en) * 2014-09-17 2014-12-03 朱忠良 Crosslinked halogen-free flame-retardant cable material

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Application publication date: 20161012