CN105037911A - Easy-peel highlighted silane crosslinking flame-retardant polyolefin insulation material, preparation method and application thereof - Google Patents
Easy-peel highlighted silane crosslinking flame-retardant polyolefin insulation material, preparation method and application thereof Download PDFInfo
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
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- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
- H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
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- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
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- C08L2205/00—Polymer mixtures characterised by other features
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- C08L2207/062—HDPE
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- C08L2207/064—VLDPE
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- C08L2207/066—LDPE (radical process)
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- C08L2312/00—Crosslinking
- C08L2312/08—Crosslinking by silane
Abstract
The invention relates to an easy-peel highlighted silane crosslinking flame-retardant polyolefin insulation material, a preparation method and application thereof, and aims to provide the polyolefin insulation material relatively good in mechanical property and electrical property. A prepared insulating layer of a low-smoke halogen-free flame-retardant cable is uniform in crosslinking, excellent in temperature endurance and easy to peel after being made into the cable, and in a high-speed paying-off situation, the cable surface is free of melt fracture, smooth, highlighted and easy to peel. The technical scheme is as follows: the polyolefin insulation material comprises an A material and a B material, wherein the A material comprises the following components: EVA, PE, a silane coupling agent, a primary antioxidant, an auxiliary antioxidant, an initiator, a compatilizer, a lubricating agent, a fire retardant and a filler; the B material comprises the following components: EVA, PE, a catalyst, a primary antioxidant, an auxiliary antioxidant, a compatilizer, a lubricating agent, a fire retardant and a filler.
Description
Technical field
The application relates to a kind of polyolefin insulation material and preparation method thereof and application, relate more particularly to crosslinked with silicane low smoke halogen-free flame-retardant polyolefin Insulating Material and Preparation Method and application that one has low cost, preferably temperature tolerance (resistance to 125 DEG C), highlighted cable surface and the easy peel property of cable insulation, belong to wire cable material technical field.
Background technology
Along with China's economic develop rapidly, each electronic product, household electrical appliances and illumination series products are fast-developing, and the processing line demand explosive growths such as the terminal line peeling off processing have been done to all kinds of in market.Particularly some high-grade cables particular requirement such as high temperature resistant, low-smoke non-halogen flame-retardant in addition.The material requirements doing such processing line is upgraded to by original PVC material can have very high insulating property, fire-retardant, high-and low-temperature resistance, machinery are wear-resisting, ageing-resistant, the crosslinking type low-smoke halogen-free environmental protection material of resist chemical, highlight surface.Consider the convenience of processing, and Cost Problems, crosslinked with silicane low smoke halogen-free flame-retardant polyolefin Insulation Material becomes the preferred material of such cable.
After existing irradiated crosslinking low-smoke and halogen-free material makes such electronic cable, irradiation processing center irradiation must be delivered to; On the one hand transport and irradiation are costly, significantly can improve cable cost, are fatal hard defects for profit own with regard to such very meagre cable; On the other hand, such cable needs the weathering test by 158 DEG C, and this experiment can judge that cable in use has the length that whether there is potential safety hazard and cable work-ing life.Because the irradiation crosslinking processes ubiquity of cable is cross-linked uneven phenomenon, so through the cable of radiation treatment, its thermotolerance can not meet long-time cable service requirements under 125 DEG C of environment preferably.
Silicane crosslinking flame retardant polyolefin cable material with low smoke halogen have crosslinked evenly, good heat resistance, and the advantage such as technique is simple, convenient for production, progressively instead of irradiated crosslinking low-smoke and halogen-free flame retardant polyolefin material in recent years.Polyolefine material because of silane-crosslinkable will use the material of the high tenacity such as a large amount of EVA, is unfavorable for the wire stripping processing of electric wire, and wire stripper is as little in edge of a knife pressurization, and material can not be peeled off, the little tail that has that can peel off causes using; If edge of a knife pressurization is too large, easily material will be cut off together with wire.In addition, such cable requires to have high brightness.Therefore, the development of the highlighted easy stripping crosslinked with silicane low smoke halogen-free flame-retardant polyolefin material of heatproof 125 DEG C has several large difficult point: one, when unwrapping wire, should make cable surface light.But because added the material of toughner, the phenomenon of slightly sub-light will be there is; How while adding toughner, highlighted cable surface is kept to be difficult point one.Two, in the wire stripping work program after unwrapping wire, how to be peeled off smoothly by the termination of line material is another difficult point.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of polyolefin insulation material and preparation method thereof and application, the polyolefin insulation material provided, good mechanical property should be had, good electrical property, the insulation layer of the low-smoke halogen-free inflaming-retarding cable made is evenly crosslinked, there is excellent temperature tolerance, easily peel off after stranding; In high speed unwinding situation, cable surface is smooth highlighted without melt fracture, cable surface, and easily shells.
The preparation method provided should be able to the easy separability of strongthener, improving the success ratio of cable when being processed into terminal line, reducing the consumption of defect ware.
Technical scheme provided by the invention is:
A kind of polyolefin insulation material, comprises A material and B material,
Described A expects that the component that comprises and corresponding weight part are:
EVA10 ~ 80, PE10 ~ 100, silane coupling agent 1 ~ 3, primary antioxidant 1 ~ 5, auxiliary anti-oxidant 1 ~ 3, initiator 0.05 ~ 0.2, compatilizer 1 ~ 20, lubricant 1 ~ 10, fire retardant 50 ~ 100, weighting agent 50 ~ 200;
Described B expects the component that comprises and corresponding weight part:
EVA10 ~ 80, PE10 ~ 100, catalyzer 0.1 ~ 3, primary antioxidant 1 ~ 5, auxiliary anti-oxidant 1 ~ 3, compatilizer 1 ~ 20, lubricant 1 ~ 10, fire retardant 50 ~ 100, weighting agent 50 ~ 200;
The part by weight that described A material and B expect is 90-97:3-10.
Described A expects that the component that comprises and corresponding weight part are:
EVA20 ~ 50, PE50 ~ 80, silane coupling agent 1 ~ 3, primary antioxidant 1 ~ 5, auxiliary anti-oxidant 1 ~ 3, initiator 0.05 ~ 0.2, compatilizer 1 ~ 20 part, lubricant 1 ~ 10 part, fire retardant 50 ~ 90, weighting agent 120 ~ 170;
Described B expects the component that comprises and corresponding weight part:
EVA20 ~ 50, PE50 ~ 80, catalyzer 0.1 ~ 3, primary antioxidant 1 ~ 5, auxiliary anti-oxidant 1 ~ 3, compatilizer 1 ~ 20, lubricant 1 ~ 10, fire retardant 60 ~ 90, weighting agent 120 ~ 170;
Described A expects that the component that comprises and corresponding weight part are:
EVA30 ~ 40, PE65 ~ 75, silane coupling agent 1 ~ 3, primary antioxidant 1 ~ 5, auxiliary anti-oxidant 1 ~ 3, initiator 0.05 ~ 0.2, compatilizer 1 ~ 20, lubricant 1 ~ 10, fire retardant 75 ~ 85, weighting agent 140 ~ 160;
Described B expects the component that comprises and corresponding weight part:
EVA30 ~ 40, PE65 ~ 75, catalyzer 0.1 ~ 3, primary antioxidant 1 ~ 5, auxiliary anti-oxidant 1 ~ 3, compatilizer 1 ~ 20, lubricant 1 ~ 10, fire retardant 75 ~ 85, weighting agent 140 ~ 160;
Described EVA is the mixture of a kind of ethylene-vinyl acetate copolymer or multiple ethylene-vinyl acetate copolymer.
Described PE is the mixing of a kind of or two or more arbitrary proportion in LDPE, LLDPE, VLDPE, ULDPE, HDPE, MDPE, MLLDPE.
In described EVA, vinyl acetate content is 14 ~ 30%.
The density of described PE is 0.860 ~ 0.950g/cm
3, be preferably 0.870 ~ 0.930g/cm
3, melting index (190 DEG C, 2.16kg) is 0.1 ~ 50g/10min, is preferably 3 ~ 5g/10min.
In described A material, silane coupling agent is vinyl silanes, is specially the mixing of one or more arbitrary proportions in vinyltriethoxysilane, vinyltrimethoxy silane, methylvinyldimethoxysilane, methyl vinyl diethoxysilane, vinyl three (2-methoxy ethoxy) silane.
During described A material and B expect, primary antioxidant is 4, 4'-thiobis (the 6-tertiary butyl-3-methylphenol), four [β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, 2, 6-ditertbutylparacresol, 2, 2'-methylene-bis (4-methyl-6-tert-butylphenol), N, N'-pair-(3-(3, 5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine, CHEMNOXB225, CHEMNOXB900, CHEMNOXB561, 2, 4, 6-tri-butyl-phenol, 1, 1, the mixing of one or more arbitrary proportions in 3-tri-(2-methyl-4-hydroxyl-5-trimethylphenylmethane base) butane.
During described A material and B expect, auxiliary anti-oxidant is three [2,4-di-tert-butyl-phenyl] phosphorous acid ester, N, N '-bis-[β-(3,5-di-tert-butyl-hydroxy phenyl) propionyl] hydrazine, distearyl thiodipropionate, the two lauryl, 3 of thio-2 acid, 5-di-tert-butyl-4-hydroxyl benzyl diethyl phosphoric acid, 1,3, the mixing of one or more arbitrary proportions in 5-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) tricarbimide, triphenyl phosphite, phosphorous acid benzene di-isooctyl, phosphorous acid dihydroxyphenyl propane.
In described A material, initiator is peroxide type initiators, as dicumyl peroxide, benzoyl peroxide, peroxidation 2 ethyl hexanoic acid tert-pentyl ester, peroxidation acetic acid tert-pentyl ester, peroxidation 3,3, the mixing of one or more arbitrary proportions in 5 trimethylhexanoate, 3,3-two (t-butyl peroxy) ethyl butyrates, di t-amyl peroxide, di-t-butyl peroxide, tertbutyl peroxide, t-amyl peroxy hydrogen.
During described A material and B expect, compatilizer is the mixing of one or more arbitrary proportions in maleic anhydride grafted polyethylene, maleic anhydride inoculated polypropylene, maleic anhydride graft EVA, acrylic acid-grafted polyethylene, maleic anhydride graft POE, Ethylene-Propylene Block Copolymer, styrene-butadiene copolymer.
During described A material and B expect, lubricant is the mixing of one or more arbitrary proportions in silicone, stearic acid, amine hydroxybenzene, PE wax, white paraffin, Zinic stearas, calcium stearate, polyethers, N, N'-ethylenebisstearamide.
During described A material and B expect, fire retardant is the mixing of one or more arbitrary proportions in aluminium hydroxide, magnesium hydroxide, zinc borate, tetramethylolmethane, hydrotalcite, brucite, magnesium oxide, antimonous oxide, barium sulfate, polynite, red phosphorus, urea, trimeric cyanamide, tripolyphosphate ammonium, expanded graphites, isocyanuric acid three-glycidyl ester.
During described A material and B expect, weighting agent is the mixing of the mixing of one or more fireproof inorganic powder arbitrary proportions such as hollow glass micropearl (10 ~ 20 μm), calcium carbonate, white carbon black, talcum powder, calcite in powder, potter's clay, diatomite, silicon-dioxide, mica powder, carbon fiber.
In described B material, catalyzer is the mixing of one or more arbitrary proportions in dibutyl tin laurate, dibutyltin diacetate, dioctyl tin two (methyl ethyl diketone) inner complex, organotin carboxylate, titanate ester.
The preparation method of described polyolefin insulation material, is characterized in that, comprising: A material and B are expected that each self-contained component is mixing, absorbs, obtained A material and B material, then by A material and the mixing of B material, and obtained described polyolefin insulation material.
Polyolefin insulation material prepared by the present invention is for the manufacture of cable.
The invention has the beneficial effects as follows: the heatproof provided 125 DEG C is the highlighted crosslinked with silicane low smoke halogen-free flame-retardant polyolefin Insulation Material of stripping easily, not only performance meets the related request of JB/T10436-2004 " electric wire crosslinkable fire retardant polyolefin material " completely, and it has good mechanical property, good electrical property, sharpest edges are that insulation layer is evenly crosslinked, have excellent temperature tolerance, obtained cable is easily shelled.In high speed unwinding situation, cable surface is without melt fracture, light.Be more suitable for temperature resistant grade high, cable surface requires high, and the low-smoke halogen-free inflaming-retarding cable of easily stripping.
Embodiment
In following examples, A-151 is vinyltriethoxysilane, antioxidant 300 is 4,4'-thiobis (the 6-tertiary butyl-3-methylphenol) (also claiming oxidation inhibitor TBM-6), AT-10 is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (also claiming antioxidant 1010), and DSTP is distearyl thiodipropionate, DCP is dicumyl peroxide, and PE-g-MAH is maleic anhydride grafted polyethylene.
Vinyl acetate (VA) content in EVA is 14 ~ 28%.
Embodiment 1: each component and weight part as follows.
Above-mentioned all components all can be commercially available from market.
First on Banbury mixer, EVA (VA content is 14%), LLDPE, AT-10, DSTP, PE-g-MAH, silicone, aluminium hydroxide, calcium carbonate is evenly mixing, and the public masterbatch that granulation is expected as A, B.Silane coupling agent, oxidation inhibitor, initiator are made into silane adjuvant, absorb silane adjuvant with masterbatch, and both obtain A material with Aluminum-plastic composite bag vacuum packaging; Absorb dibutyl tin laurate with masterbatch, and with Aluminum-plastic composite bag pack both B material.
A material and B material are merged (A material: B material=95:5 (weight ratio)), obtain polyolefin insulation material.
Embodiment 2: each component and weight part as follows.
Polyolefin insulation material is prepared, wherein A material: B material=96:4 (weight ratio) according to the method identical with embodiment 1.
Embodiment 3: each component and weight part as follows.
Polyolefin insulation material is prepared, wherein A material: B material=95:5 (weight ratio) according to the method identical with embodiment 1.
Embodiment 4: each component and weight part as follows.
Polyolefin insulation material is prepared, wherein A material: B material=92:8 (weight ratio) according to the method identical with embodiment 1.
Embodiment 5: each component and weight part as follows.
Polyolefin insulation material is prepared, wherein A material: B material=91:9 (weight ratio) according to the method identical with embodiment 1.
Embodiment 6: each component and weight part as follows.
Polyolefin insulation material is prepared, wherein A material: B material=90:10 (weight ratio) according to the method identical with embodiment 1.
Embodiment 7: each component and weight part as follows.
Polyolefin insulation material is prepared, wherein A material: B material=96:4 (weight ratio) according to the method identical with embodiment 1.
Embodiment 8: each component and weight part as follows.
Polyolefin insulation material is prepared, wherein A material: B material=97:3 (weight ratio) according to the method identical with embodiment 1.
The performance number of the conventional heatproof of table 1 125 DEG C of crosslinked with silicane fire retardant polyolefin Insulation Material (YJZG-125)
In table 1, "-" indicates without corresponding requirements value.
The performance number (measuring method is with table 1) of the polyolefin insulation material of table 2 embodiment of the present invention 1-8
As can be seen from upper table data, the performance of each material of embodiment 1 ~ 8 gained meets the requirement of the YJZG-125 in JB/T10436-2004 " electric wire crosslinkable polyethylene Insulation Material " completely, and unwrapping wire highlight surface, institute's cable that does easily is shelled when processing terminal line, and there is very high insulating property and feature that is fire-retardant, high temperature resistant, low temperature resistant, wear-resisting, ageing-resistant, the resist chemical of machinery, can meet the need of market completely.
Claims (10)
1. a polyolefin insulation material, comprises A material and B material,
Described A expects that the component that comprises and corresponding weight part are:
EVA10 ~ 80, PE10 ~ 100, silane coupling agent 1 ~ 3, primary antioxidant 1 ~ 5, auxiliary anti-oxidant 1 ~ 3, initiator 0.05 ~ 0.2, compatilizer 1 ~ 20, lubricant 1 ~ 10, fire retardant 50 ~ 100, weighting agent 50 ~ 200;
Described B expects the component that comprises and corresponding weight part:
EVA10 ~ 80, PE10 ~ 100, catalyzer 0.1 ~ 3, primary antioxidant 1 ~ 5, auxiliary anti-oxidant 1 ~ 3, compatilizer 1 ~ 20, lubricant 1 ~ 10, fire retardant 50 ~ 100, weighting agent 50 ~ 200;
The part by weight that described A material and B expect is 90-97:3-10;
Described EVA is the mixture of a kind of ethylene-vinyl acetate copolymer or multiple ethylene-vinyl acetate copolymer;
Described PE is the mixing of a kind of or two or more arbitrary proportion in LDPE, LLDPE, VLDPE, ULDPE, HDPE, MDPE, MLLDPE;
In described A material, silane coupling agent is the mixing of one or more arbitrary proportions in vinyltriethoxysilane, vinyltrimethoxy silane, methylvinyldimethoxysilane, methyl vinyl diethoxysilane, vinyl three (2-methoxy ethoxy) silane;
During described A material and B expect, weighting agent is the mixing of the mixing of one or more fireproof inorganic powder arbitrary proportions such as hollow glass micropearl (10 ~ 20 μm), calcium carbonate, white carbon black, talcum powder, calcite in powder, potter's clay, diatomite, silicon-dioxide, mica powder, carbon fiber;
During described A material and B expect, fire retardant is the mixing of one or more arbitrary proportions in aluminium hydroxide, magnesium hydroxide, zinc borate, tetramethylolmethane, hydrotalcite, brucite, magnesium oxide, antimonous oxide, barium sulfate, polynite, red phosphorus, urea, trimeric cyanamide, tripolyphosphate ammonium, expanded graphites, isocyanuric acid three-glycidyl ester;
During described A material and B expect, compatilizer is the mixing of one or more arbitrary proportions in maleic anhydride grafted polyethylene, maleic anhydride inoculated polypropylene, maleic anhydride graft EVA, acrylic acid-grafted polyethylene, maleic anhydride graft POE, Ethylene-Propylene Block Copolymer, styrene-butadiene copolymer.
2. polyolefin insulation material according to claim 1, is characterized in that:
Described A expects that the component that comprises and corresponding weight part are:
EVA20 ~ 50, PE50 ~ 80, silane coupling agent 1 ~ 3, primary antioxidant 1 ~ 5, auxiliary anti-oxidant 1 ~ 3, initiator 0.05 ~ 0.2, compatilizer 1 ~ 20 part, lubricant 1 ~ 10 part, fire retardant 60 ~ 90, weighting agent 120 ~ 170;
Described B expects the component that comprises and corresponding weight part:
EVA20 ~ 50, PE50 ~ 80, catalyzer 0.1 ~ 3, primary antioxidant 1 ~ 5, auxiliary anti-oxidant 1 ~ 3, compatilizer 1 ~ 20, lubricant 1 ~ 10, fire retardant 60 ~ 90, weighting agent 120 ~ 170.
3. polyolefin insulation material according to claim 1, is characterized in that:
Described A expects that the component that comprises and corresponding weight part are:
EVA30 ~ 40, PE65 ~ 75, silane coupling agent 1 ~ 3, primary antioxidant 1 ~ 5, auxiliary anti-oxidant 1 ~ 3, initiator 0.05 ~ 0.2, compatilizer 1 ~ 20, lubricant 1 ~ 10, fire retardant 75 ~ 85, weighting agent 140 ~ 160;
Described B expects the component that comprises and corresponding weight part:
EVA30 ~ 40, PE65 ~ 75, catalyzer 0.1 ~ 3, primary antioxidant 1 ~ 5, auxiliary anti-oxidant 1 ~ 3, compatilizer 1 ~ 20, lubricant 1 ~ 10, fire retardant 75 ~ 85, weighting agent 140 ~ 160.
4. the polyolefin insulation material according to claim 1 or 2 or 3, is characterized in that:
During described A material and B expect, primary antioxidant is 4, 4'-thiobis (the 6-tertiary butyl-3-methylphenol), four [β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, 2, 6-ditertbutylparacresol, 2, 2'-methylene-bis (4-methyl-6-tert-butylphenol), N, N'-pair-(3-(3, 5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine, CHEMNOXB225, CHEMNOXB900, CHEMNOXB561, 2, 4, 6-tri-butyl-phenol, 1, 1, the mixing of one or more arbitrary proportions in 3-tri-(2-methyl-4-hydroxyl-5-trimethylphenylmethane base) butane.
5. the polyolefin insulation material according to claim 1 or 2 or 3, is characterized in that:
During described A material and B expect, auxiliary anti-oxidant is three [2,4-di-tert-butyl-phenyl] phosphorous acid ester, N, N '-bis-[β-(3,5-di-tert-butyl-hydroxy phenyl) propionyl] hydrazine, distearyl thiodipropionate, the two lauryl, 3 of thio-2 acid, 5-di-tert-butyl-4-hydroxyl benzyl diethyl phosphoric acid, 1,3, the mixing of one or more arbitrary proportions in 5-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) tricarbimide, triphenyl phosphite, phosphorous acid benzene di-isooctyl, phosphorous acid dihydroxyphenyl propane.
6. the polyolefin insulation material according to claim 1 or 2 or 3, is characterized in that:
In described A material, initiator is peroxide type initiators, as dicumyl peroxide, benzoyl peroxide, peroxidation 2 ethyl hexanoic acid tert-pentyl ester, peroxidation acetic acid tert-pentyl ester, peroxidation 3,3, the mixing of one or more arbitrary proportions in 5 trimethylhexanoate, 3,3-two (t-butyl peroxy) ethyl butyrates, di t-amyl peroxide, di-t-butyl peroxide, tertbutyl peroxide, t-amyl peroxy hydrogen.
7. the polyolefin insulation material according to claim 1 or 2 or 3, is characterized in that:
During described A material and B expect, lubricant is the mixing of one or more arbitrary proportions in silicone, stearic acid, amine hydroxybenzene, PE wax, white paraffin, Zinic stearas, calcium stearate, polyethers, N, N'-ethylenebisstearamide.
8. the polyolefin insulation material according to claim 1 or 2 or 3, is characterized in that:
In described B material, catalyzer is the mixing of one or more arbitrary proportions in dibutyl tin laurate, dibutyltin diacetate, dioctyl tin two (methyl ethyl diketone) inner complex, organotin carboxylate, titanate ester.
9. the preparation method of polyolefin insulation material according to claim 1, comprising: A material and B are expected that each self-contained component is mixing, absorbs, obtained A material and B material, then by A material and the mixing of B material, and obtained described polyolefin insulation material.
10. polyolefin insulation material according to claim 1 is for the manufacture of cable.
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