CN111793264A - Irradiation crosslinking halogen-free low-smoke flame-retardant power cable - Google Patents
Irradiation crosslinking halogen-free low-smoke flame-retardant power cable Download PDFInfo
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- CN111793264A CN111793264A CN202010753006.1A CN202010753006A CN111793264A CN 111793264 A CN111793264 A CN 111793264A CN 202010753006 A CN202010753006 A CN 202010753006A CN 111793264 A CN111793264 A CN 111793264A
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 87
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000000779 smoke Substances 0.000 title claims abstract description 32
- 238000004132 cross linking Methods 0.000 title claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 71
- 238000002156 mixing Methods 0.000 claims abstract description 44
- -1 polyethylene Polymers 0.000 claims abstract description 42
- 239000004698 Polyethylene Substances 0.000 claims abstract description 40
- 229920000573 polyethylene Polymers 0.000 claims abstract description 40
- 239000002131 composite material Substances 0.000 claims abstract description 33
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000004020 conductor Substances 0.000 claims abstract description 17
- 238000001816 cooling Methods 0.000 claims abstract description 17
- 229920006124 polyolefin elastomer Polymers 0.000 claims abstract description 16
- 238000002844 melting Methods 0.000 claims abstract description 9
- 230000008018 melting Effects 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000002250 absorbent Substances 0.000 claims abstract description 7
- 230000002745 absorbent Effects 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 48
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims description 36
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 33
- 229920001684 low density polyethylene Polymers 0.000 claims description 25
- 239000004702 low-density polyethylene Substances 0.000 claims description 25
- 239000012046 mixed solvent Substances 0.000 claims description 24
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical group OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 claims description 24
- 229920005989 resin Polymers 0.000 claims description 24
- 239000011347 resin Substances 0.000 claims description 24
- 239000003963 antioxidant agent Substances 0.000 claims description 23
- 230000003078 antioxidant effect Effects 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 18
- 244000223014 Syzygium aromaticum Species 0.000 claims description 16
- 235000016639 Syzygium aromaticum Nutrition 0.000 claims description 16
- 239000000341 volatile oil Substances 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 229940011182 cobalt acetate Drugs 0.000 claims description 12
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- 238000005469 granulation Methods 0.000 claims description 12
- 230000003179 granulation Effects 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 10
- 230000001678 irradiating effect Effects 0.000 claims description 9
- 238000004513 sizing Methods 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 238000007873 sieving Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 230000005855 radiation Effects 0.000 claims description 3
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 238000002485 combustion reaction Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 229920013716 polyethylene resin Polymers 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 4
- 238000007792 addition Methods 0.000 description 3
- 230000000844 anti-bacterial effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 229920003020 cross-linked polyethylene Polymers 0.000 description 1
- 239000004703 cross-linked polyethylene Substances 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229940124543 ultraviolet light absorber Drugs 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
- C08L23/02—Compositions 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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/003—Apparatus or processes specially adapted for manufacturing conductors or cables using irradiation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/06—Insulating conductors or cables
- H01B13/14—Insulating conductors or cables by extrusion
- H01B13/148—Selection of the insulating material therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/22—Sheathing; Armouring; Screening; Applying other protective layers
- H01B13/24—Sheathing; Armouring; Screening; Applying other protective layers by extrusion
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
- H01B7/18—Protection against damage caused by wear, mechanical force or pressure; Sheaths; Armouring
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
- H01B7/29—Protection against damage caused by extremes of temperature or by flame
- H01B7/295—Protection against damage caused by extremes of temperature or by flame using material resistant to flame
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B9/00—Power cables
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
- C08L2312/06—Crosslinking by radiation
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Organic Insulating Materials (AREA)
Abstract
The invention discloses an irradiation crosslinking halogen-free low-smoke flame-retardant power cable which comprises the following raw materials in parts by weight: 55-70 parts of modified polyethylene, 30-35 parts of composite halogen-free flame retardant, 0.8-2 parts of ultraviolet absorbent, 1-5 parts of KH550 and 25-40 parts of polyolefin elastomer; firstly, adding modified polyethylene, a composite halogen-free flame retardant, a polyolefin elastomer, an ultraviolet absorbent and KH550 into an internal mixer, uniformly mixing, and taking out after internal mixing is finished to prepare a cable material; secondly, melting, plasticizing and extruding the cable material through an extruder, cooling with water, granulating, extruding through the extruder again, and wrapping the surface of the conductor to obtain the irradiation crosslinking halogen-free low-smoke flame-retardant power cable; the complex in the composite halogen-free flame retardant can be used as a synergistic flame retardant, and can reduce the consumption of the MPP flame retardant when matched with the MPP flame retardant, increase the residual carbon content during combustion and increase the flame retardant effect.
Description
Technical Field
The invention belongs to the technical field of power cable preparation, and particularly relates to an irradiation crosslinking halogen-free low-smoke flame-retardant power cable.
Background
Polyolefin is used as a main raw material, a proper amount of reinforced crosslinking photoinitiation system is added, ultraviolet light is used for irradiating under a certain condition, a photoinitiator absorbs ultraviolet light with a specific wavelength to initiate and generate active macromolecular free radicals, and independent polyethylene long-chain macromolecules are connected into a three-dimensional reticular crosslinked polyethylene supermolecule structure by chemical bonds through serial rapid crosslinking reaction of the macromolecular free radicals and other additives. The cross-linked polyolefin material has excellent high temperature resistance, solvent resistance, excellent electrical performance, obviously enhanced mechanical performance and the like. The ultraviolet radiation processing technology is to irradiate the high molecular material under normal pressure in a molten state after the high molecular material is extruded, so that the material is not damaged, the efficiency and the energy are high, the light can deeply enter the polymer to act, no residual toxicity or waste is caused, the control method is simple and convenient, and the ultraviolet radiation processing technology is suitable for industrialized and large-scale production.
The Chinese invention patent CN109485961A discloses an ultraviolet irradiation crosslinking cable material, which comprises the following components in parts by weight: 20-50 parts of high-density polyethylene, 80-100 parts of low-density polyethylene, 30-50 parts of flame retardant, 6-8 parts of melamine cyanurate, 2-4 parts of epoxidized soybean oil, 0.5-5 parts of ultraviolet light absorber, 0.2-0.5 part of coupling agent, 1-5 parts of antioxidant and 0.2-0.4 part of stearic acid.
Disclosure of Invention
In order to overcome the technical problems, the invention provides an irradiation crosslinking halogen-free low-smoke flame-retardant power cable.
The technical problems to be solved by the invention are as follows:
in the prior art, an antioxidant is added into polyethylene, and the antioxidant can weaken intermolecular force of molecular chains in polyethylene resin, so that the tensile strength of the polyethylene resin is reduced, and the mechanical strength of the prepared cable material is low.
The purpose of the invention can be realized by the following technical scheme:
an irradiation crosslinking halogen-free low-smoke flame-retardant power cable comprises the following raw materials in parts by weight: 55-70 parts of modified polyethylene, 30-35 parts of composite halogen-free flame retardant, 0.8-2 parts of ultraviolet absorbent, 1-5 parts of KH550 and 25-40 parts of polyolefin elastomer;
the irradiation crosslinking halogen-free low-smoke flame-retardant power cable is prepared by the following method:
firstly, adding modified polyethylene, a composite halogen-free flame retardant, a polyolefin elastomer, an ultraviolet absorbent and KH550 into an internal mixer, uniformly mixing, and taking out after internal mixing is finished to prepare a cable material;
and secondly, melting, plasticizing and extruding the cable material through an extruder, performing water cooling and granulation, extruding the material through the extruder again, wrapping the material on the surface of the conductor, and irradiating the conductor in an ultraviolet irradiation machine after traction, cooling, sizing and coiling, wherein the irradiation energy is controlled to be 5-15Mrad, so that the irradiation crosslinking halogen-free low-smoke flame-retardant power cable is prepared.
Further, the ultraviolet absorbent is 2-hydroxy-4-n-octoxybenzophenone.
Further, the composite halogen-free flame retardant is prepared by the following method:
step S1, adding salicylaldehyde into a sodium hydroxide aqueous solution with the mass fraction of 10%, uniformly stirring for 15min, transferring to a three-neck flask, heating in a water bath at 35-40 ℃, magnetically stirring for 20min, then dropwise adding a hydrogen peroxide aqueous solution with the mass fraction of 30%, controlling the dropwise adding time to be 30-45min, then heating to 45-50 ℃, continuing stirring for 10min, centrifuging, filtering, transferring to an oven with the temperature of 85-90 ℃ for drying for 4-5h, preparing a material A, and controlling the amount ratio of salicylaldehyde to sodium hydroxide to hydrogen peroxide to be 1: 0.5: 1;
step S2, uniformly mixing methanol and deionized water according to a weight ratio of 1: 10 to prepare a mixed solvent, adding the material A into one half of the mixed solvent, magnetically stirring for 10min to prepare a mixed solution B, adding cobalt acetate into the other half of the mixed solvent, uniformly stirring to prepare a solution C, dropwise adding the solution C into the mixed solution B, controlling the dropwise adding time to be 30min, refluxing, condensing and stirring for 10min at 70 ℃ to prepare a complex, filtering, and drying in an oven at 90 ℃ for 4-5 h;
and step S3, mixing the dried complex with MPP according to the weight ratio of 1: 1 to prepare the composite halogen-free flame retardant.
Step S1, firstly adding salicylaldehyde into a sodium hydroxide aqueous solution, then dropwise adding the aqueous hydrogen peroxide solution, wherein the aqueous hydrogen peroxide solution is used as an oxidant, the mass fraction of the aqueous hydrogen peroxide solution is controlled to be 30%, active oxygen ions are generated in the aqueous solution under the concentration, the salicylaldehyde can be oxidized to prepare a material A, the material A is an oligomeric salicylaldehyde precursor, a complex is prepared in step S2, the reaction temperature is controlled to be 70 ℃, the situation that molecules in a system cannot absorb enough energy in the reaction process to cause violent collision can be prevented, the reaction process is slow, the yield is low, the complex and MPP are mixed according to the weight ratio of 1: 1 in step S3 to prepare the composite halogen-free flame retardant, the complex can be used as a synergistic flame retardant, the dosage of the MPP flame retardant can be reduced on one hand, and the technical problem that the mechanical property of a base material is reduced due to the addition of the flame retardant into the base, on the other hand, the residual carbon amount can be increased during combustion, and the flame retardant effect is increased.
Further, in the step S2, the weight ratio of the material A, the cobalt acetate and the mixed solvent is controlled to be 1: 10: 0.2-0.3.
Further, the modified polyethylene is prepared by the following method:
vacuum drying low-density polyethylene resin for 4-5h, controlling the vacuum degree at-0.10 MPa and the temperature at 60-70 ℃, then grinding and crushing an antioxidant, sieving with a 200-mesh sieve, mixing the dried low-density polyethylene resin with the crushed antioxidant, magnetically stirring for 30-45min, adding clove essential oil, continuously stirring for 10-15min, then blending, extruding and granulating through a double-screw extruder to obtain modified polyethylene, and controlling the weight ratio of the low-density polyethylene resin to the antioxidant to the clove essential oil to be 10: 0.1: 0.05.
In the prior art, an antioxidant is added into polyethylene, and the antioxidant can weaken intermolecular force of molecular chains in polyethylene resin, so that the tensile strength of the polyethylene resin is reduced, and the mechanical strength of the prepared cable material is low; according to the invention, the low-density polyethylene resin is dried in vacuum for 4-5h, then the antioxidant is ground and crushed, mixed with the low-density polyethylene resin and added with the clove essential oil, and then the mixture is blended and extruded, so that the crystallinity of the polyethylene resin can be improved by the clove essential oil, the mechanical strength of the modified polyethylene is further improved, and the clove essential oil can endow the modified polyethylene with a certain antibacterial effect.
Further, the antioxidant is one or two of an antioxidant 1010 or an antioxidant 168 which are mixed according to any proportion.
The invention has the beneficial effects that:
(1) the irradiation crosslinking halogen-free low-smoke flame-retardant power cable is prepared from raw materials such as modified polyethylene and a composite halogen-free flame retardant, and in the prior art, an antioxidant is added into polyethylene, and the antioxidant can weaken intermolecular force of molecular chains in polyethylene resin, so that the tensile strength of the polyethylene resin is reduced, and the mechanical strength of the prepared cable material is low; the preparation method comprises the steps of firstly drying the low-density polyethylene resin in vacuum for 4-5h, then grinding and crushing the antioxidant, mixing the antioxidant with the low-density polyethylene resin, adding clove essential oil, blending and extruding, wherein the clove essential oil can improve the crystallinity of the polyethylene resin, so that the mechanical strength of the modified polyethylene is improved, and the clove essential oil can endow the modified polyethylene with a certain antibacterial effect, so that the power cable prepared by the preparation method disclosed by the invention has excellent mechanical strength;
(2) the invention also provides a composite halogen-free flame retardant, in the preparation process, in step S1, salicylaldehyde is firstly added into a sodium hydroxide aqueous solution, then the hydrogen peroxide aqueous solution is dropwise added, the hydrogen peroxide aqueous solution is used as an oxidant, the mass fraction of the hydrogen peroxide aqueous solution is controlled to be 30%, active oxygen ions are generated in the solution under the concentration, the salicylaldehyde can be oxidized to prepare a material A, the material A is an oligomeric salicylaldehyde precursor, in step S2, a complex is prepared, the reaction temperature is controlled to be 70 ℃, the situation that enough energy cannot be absorbed among molecules in a system in the reaction process to carry out violent collision can be prevented, the reaction process is too slow, the yield is low, in step S3, the complex and MPP are mixed according to the weight ratio of 1: 1 to prepare the composite halogen-free flame retardant, the complex can be used as a synergistic flame retardant, on one hand, the dosage of the MPP flame, the technical problem that the mechanical property of the base material is reduced due to the fact that the flame retardant is added into the base material is solved, and on the other hand, the residual carbon quantity can be increased during combustion, and the flame retardant effect is improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
An irradiation crosslinking halogen-free low-smoke flame-retardant power cable comprises the following raw materials in parts by weight: 55 parts of modified polyethylene, 30 parts of a composite halogen-free flame retardant, 0.8 part of 2-hydroxy-4-n-octoxy benzophenone, 1 part of KH550 and 25 parts of a polyolefin elastomer;
the irradiation crosslinking halogen-free low-smoke flame-retardant power cable is prepared by the following method:
firstly, adding modified polyethylene, a composite halogen-free flame retardant, a polyolefin elastomer, 2-hydroxy-4-n-octoxy benzophenone and KH550 into an internal mixer, uniformly mixing, and taking out after internal mixing is finished to prepare a cable material;
and secondly, melting, plasticizing and extruding the cable material through an extruder, performing water cooling and granulation, extruding the material through the extruder again, wrapping the material on the surface of the conductor, and irradiating the conductor in an ultraviolet irradiation machine after traction, cooling, sizing and coiling, wherein the irradiation energy is controlled to be 10Mrad, so that the irradiation cross-linked halogen-free low-smoke flame-retardant power cable is prepared.
The composite halogen-free flame retardant is prepared by the following method:
step S1, adding salicylaldehyde into a 10 mass percent sodium hydroxide aqueous solution, uniformly stirring for 15min, transferring to a three-neck flask, heating in a water bath at 35 ℃, magnetically stirring for 20min, then dropwise adding a 30 mass percent hydrogen peroxide aqueous solution, controlling the dropwise adding time to be 30min, then heating to 45 ℃, continuing stirring for 10min, centrifuging, filtering, transferring to an oven at 85 ℃ for drying for 4h, and preparing a material A, wherein the mass ratio of salicylaldehyde to sodium hydroxide to hydrogen peroxide is controlled to be 1: 0.5: 1;
step S2, uniformly mixing methanol and deionized water according to the weight ratio of 1: 10 to prepare a mixed solvent, adding a material A into one half of the mixed solvent, magnetically stirring for 10min to prepare a mixed solution B, adding cobalt acetate into the other half of the mixed solvent, uniformly stirring to prepare a solution C, then dropwise adding the solution C into the mixed solution B, controlling the dropwise adding time to be 30min, refluxing, condensing and stirring for 10min at 70 ℃, preparing a complex, filtering, and drying in an oven at 90 ℃ for 4h, wherein the weight ratio of the material A, the cobalt acetate and the mixed solvent is controlled to be 1: 10: 0.2;
and step S3, mixing the dried complex with MPP according to the weight ratio of 1: 1 to prepare the composite halogen-free flame retardant.
The modified polyethylene is prepared by the following method:
vacuum drying low-density polyethylene resin for 4h, controlling the vacuum degree to be-0.10 MPa and the temperature to be 60 ℃, then grinding and crushing an antioxidant 1010, sieving by a 200-mesh sieve, mixing the dried low-density polyethylene resin with the crushed antioxidant, magnetically stirring for 30min, adding clove essential oil, continuously stirring for 10min, then performing blending extrusion and granulation by a double-screw extruder to prepare modified polyethylene, and controlling the weight ratio of the low-density polyethylene resin to the antioxidant 1010 to be 10: 0.1: 0.05.
Example 2
An irradiation crosslinking halogen-free low-smoke flame-retardant power cable comprises the following raw materials in parts by weight: 60 parts of modified polyethylene, 32 parts of composite halogen-free flame retardant, 1 part of 2-hydroxy-4-n-octoxy benzophenone, 2 parts of KH550 and 30 parts of polyolefin elastomer;
the irradiation crosslinking halogen-free low-smoke flame-retardant power cable is prepared by the following method:
firstly, adding modified polyethylene, a composite halogen-free flame retardant, a polyolefin elastomer, 2-hydroxy-4-n-octoxy benzophenone and KH550 into an internal mixer, uniformly mixing, and taking out after internal mixing is finished to prepare a cable material;
and secondly, melting, plasticizing and extruding the cable material through an extruder, performing water cooling and granulation, extruding the material through the extruder again, wrapping the material on the surface of the conductor, and irradiating the conductor in an ultraviolet irradiation machine after traction, cooling, sizing and coiling, wherein the irradiation energy is controlled to be 10Mrad, so that the irradiation cross-linked halogen-free low-smoke flame-retardant power cable is prepared.
The composite halogen-free flame retardant is prepared by the following method:
step S1, adding salicylaldehyde into a 10 mass percent sodium hydroxide aqueous solution, uniformly stirring for 15min, transferring to a three-neck flask, heating in a water bath at 35 ℃, magnetically stirring for 20min, then dropwise adding a 30 mass percent hydrogen peroxide aqueous solution, controlling the dropwise adding time to be 30min, then heating to 45 ℃, continuing stirring for 10min, centrifuging, filtering, transferring to an oven at 85 ℃ for drying for 4h, and preparing a material A, wherein the mass ratio of salicylaldehyde to sodium hydroxide to hydrogen peroxide is controlled to be 1: 0.5: 1;
step S2, uniformly mixing methanol and deionized water according to the weight ratio of 1: 10 to prepare a mixed solvent, adding a material A into one half of the mixed solvent, magnetically stirring for 10min to prepare a mixed solution B, adding cobalt acetate into the other half of the mixed solvent, uniformly stirring to prepare a solution C, then dropwise adding the solution C into the mixed solution B, controlling the dropwise adding time to be 30min, refluxing, condensing and stirring for 10min at 70 ℃, preparing a complex, filtering, and drying in an oven at 90 ℃ for 4h, wherein the weight ratio of the material A, the cobalt acetate and the mixed solvent is controlled to be 1: 10: 0.2;
and step S3, mixing the dried complex with MPP according to the weight ratio of 1: 1 to prepare the composite halogen-free flame retardant.
The modified polyethylene is prepared by the following method:
vacuum drying low-density polyethylene resin for 4h, controlling the vacuum degree to be-0.10 MPa and the temperature to be 60 ℃, then grinding and crushing an antioxidant 1010, sieving by a 200-mesh sieve, mixing the dried low-density polyethylene resin with the crushed antioxidant, magnetically stirring for 30min, adding clove essential oil, continuously stirring for 10min, then performing blending extrusion and granulation by a double-screw extruder to prepare modified polyethylene, and controlling the weight ratio of the low-density polyethylene resin to the antioxidant 1010 to be 10: 0.1: 0.05.
Example 3
An irradiation crosslinking halogen-free low-smoke flame-retardant power cable comprises the following raw materials in parts by weight: 65 parts of modified polyethylene, 34 parts of a composite halogen-free flame retardant, 1.5 parts of 2-hydroxy-4-n-octoxy benzophenone, 4 parts of KH550 and 35 parts of a polyolefin elastomer;
the irradiation crosslinking halogen-free low-smoke flame-retardant power cable is prepared by the following method:
firstly, adding modified polyethylene, a composite halogen-free flame retardant, a polyolefin elastomer, 2-hydroxy-4-n-octoxy benzophenone and KH550 into an internal mixer, uniformly mixing, and taking out after internal mixing is finished to prepare a cable material;
and secondly, melting, plasticizing and extruding the cable material through an extruder, performing water cooling and granulation, extruding the material through the extruder again, wrapping the material on the surface of the conductor, and irradiating the conductor in an ultraviolet irradiation machine after traction, cooling, sizing and coiling, wherein the irradiation energy is controlled to be 10Mrad, so that the irradiation cross-linked halogen-free low-smoke flame-retardant power cable is prepared.
The composite halogen-free flame retardant is prepared by the following method:
step S1, adding salicylaldehyde into a 10 mass percent sodium hydroxide aqueous solution, uniformly stirring for 15min, transferring to a three-neck flask, heating in a water bath at 35 ℃, magnetically stirring for 20min, then dropwise adding a 30 mass percent hydrogen peroxide aqueous solution, controlling the dropwise adding time to be 30min, then heating to 45 ℃, continuing stirring for 10min, centrifuging, filtering, transferring to an oven at 85 ℃ for drying for 4h, and preparing a material A, wherein the mass ratio of salicylaldehyde to sodium hydroxide to hydrogen peroxide is controlled to be 1: 0.5: 1;
step S2, uniformly mixing methanol and deionized water according to the weight ratio of 1: 10 to prepare a mixed solvent, adding a material A into one half of the mixed solvent, magnetically stirring for 10min to prepare a mixed solution B, adding cobalt acetate into the other half of the mixed solvent, uniformly stirring to prepare a solution C, then dropwise adding the solution C into the mixed solution B, controlling the dropwise adding time to be 30min, refluxing, condensing and stirring for 10min at 70 ℃, preparing a complex, filtering, and drying in an oven at 90 ℃ for 4h, wherein the weight ratio of the material A, the cobalt acetate and the mixed solvent is controlled to be 1: 10: 0.2;
and step S3, mixing the dried complex with MPP according to the weight ratio of 1: 1 to prepare the composite halogen-free flame retardant.
The modified polyethylene is prepared by the following method:
vacuum drying low-density polyethylene resin for 4h, controlling the vacuum degree to be-0.10 MPa and the temperature to be 60 ℃, then grinding and crushing an antioxidant 1010, sieving by a 200-mesh sieve, mixing the dried low-density polyethylene resin with the crushed antioxidant, magnetically stirring for 30min, adding clove essential oil, continuously stirring for 10min, then performing blending extrusion and granulation by a double-screw extruder to prepare modified polyethylene, and controlling the weight ratio of the low-density polyethylene resin to the antioxidant 1010 to be 10: 0.1: 0.05.
Example 4
An irradiation crosslinking halogen-free low-smoke flame-retardant power cable comprises the following raw materials in parts by weight: 70 parts of modified polyethylene, 35 parts of composite halogen-free flame retardant, 2 parts of 2-hydroxy-4-n-octoxy benzophenone, 5 parts of KH550, and 25-40 parts of polyolefin elastomer;
the irradiation crosslinking halogen-free low-smoke flame-retardant power cable is prepared by the following method:
firstly, adding modified polyethylene, a composite halogen-free flame retardant, a polyolefin elastomer, 2-hydroxy-4-n-octoxy benzophenone and KH550 into an internal mixer, uniformly mixing, and taking out after internal mixing is finished to prepare a cable material;
and secondly, melting, plasticizing and extruding the cable material through an extruder, performing water cooling and granulation, extruding the material through the extruder again, wrapping the material on the surface of the conductor, and irradiating the conductor in an ultraviolet irradiation machine after traction, cooling, sizing and coiling, wherein the irradiation energy is controlled to be 10Mrad, so that the irradiation cross-linked halogen-free low-smoke flame-retardant power cable is prepared.
The composite halogen-free flame retardant is prepared by the following method:
step S1, adding salicylaldehyde into a 10 mass percent sodium hydroxide aqueous solution, uniformly stirring for 15min, transferring to a three-neck flask, heating in a water bath at 35 ℃, magnetically stirring for 20min, then dropwise adding a 30 mass percent hydrogen peroxide aqueous solution, controlling the dropwise adding time to be 30min, then heating to 45 ℃, continuing stirring for 10min, centrifuging, filtering, transferring to an oven at 85 ℃ for drying for 4h, and preparing a material A, wherein the mass ratio of salicylaldehyde to sodium hydroxide to hydrogen peroxide is controlled to be 1: 0.5: 1;
step S2, uniformly mixing methanol and deionized water according to the weight ratio of 1: 10 to prepare a mixed solvent, adding a material A into one half of the mixed solvent, magnetically stirring for 10min to prepare a mixed solution B, adding cobalt acetate into the other half of the mixed solvent, uniformly stirring to prepare a solution C, then dropwise adding the solution C into the mixed solution B, controlling the dropwise adding time to be 30min, refluxing, condensing and stirring for 10min at 70 ℃, preparing a complex, filtering, and drying in an oven at 90 ℃ for 4h, wherein the weight ratio of the material A, the cobalt acetate and the mixed solvent is controlled to be 1: 10: 0.2;
and step S3, mixing the dried complex with MPP according to the weight ratio of 1: 1 to prepare the composite halogen-free flame retardant.
The modified polyethylene is prepared by the following method:
vacuum drying low-density polyethylene resin for 4h, controlling the vacuum degree to be-0.10 MPa and the temperature to be 60 ℃, then grinding and crushing an antioxidant 1010, sieving by a 200-mesh sieve, mixing the dried low-density polyethylene resin with the crushed antioxidant, magnetically stirring for 30min, adding clove essential oil, continuously stirring for 10min, then performing blending extrusion and granulation by a double-screw extruder to prepare modified polyethylene, and controlling the weight ratio of the low-density polyethylene resin to the antioxidant 1010 to be 10: 0.1: 0.05.
Comparative example 1
Compared with the embodiment 1, the MPP flame retardant is used for replacing the composite halogen-free flame retardant, and the preparation method is as follows:
firstly, adding modified polyethylene, an MPP flame retardant, a polyolefin elastomer, 2-hydroxy-4-n-octoxy benzophenone and KH550 into an internal mixer, uniformly mixing, and taking out after internal mixing is finished to prepare a cable material;
and secondly, melting, plasticizing and extruding the cable material through an extruder, performing water cooling and granulation, extruding the material through the extruder again, wrapping the material on the surface of the conductor, and irradiating the conductor in an ultraviolet irradiation machine after traction, cooling, sizing and coiling, wherein the irradiation energy is controlled to be 10Mrad, so that the irradiation cross-linked halogen-free low-smoke flame-retardant power cable is prepared.
Comparative example 2
In this comparative example, no modification of the polyethylene was made compared to example 1, and the preparation was as follows:
firstly, adding polyethylene, a composite halogen-free flame retardant, a polyolefin elastomer, 2-hydroxy-4-n-octoxy benzophenone and KH550 into an internal mixer, uniformly mixing, and taking out after internal mixing is finished to prepare a cable material;
and secondly, melting, plasticizing and extruding the cable material through an extruder, performing water cooling and granulation, extruding the material through the extruder again, wrapping the material on the surface of the conductor, and irradiating the conductor in an ultraviolet irradiation machine after traction, cooling, sizing and coiling, wherein the irradiation energy is controlled to be 10Mrad, so that the irradiation cross-linked halogen-free low-smoke flame-retardant power cable is prepared.
Comparative example 3
This comparative example is a flame retardant power cable in the market.
The flame retardant grades and the strength and elongation of examples 1 to 4 and comparative examples 1 to 3 were measured, and the results are shown in the following table;
strength and elongation: the strength and elongation were measured by sampling according to ASTM D-2756 method C.
As can be seen from the above table, examples 1-4 had a flame retardant rating of V0, a strength of 32-35MPa, and an elongation of 328-365%, comparative examples 1-3 had a flame retardant rating of V1-V0, a strength of 22-28MPa, and an elongation of 95-185%; therefore, the low-density polyethylene resin is dried in vacuum for 4-5 hours, then the antioxidant is ground and crushed, mixed with the low-density polyethylene resin and added with the clove essential oil, and then the mixture is extruded, the clove essential oil can improve the crystallinity of the polyethylene resin, further improve the mechanical strength of the modified polyethylene, and endow the modified polyethylene with a certain antibacterial effect, so that the power cable prepared by the invention has excellent mechanical strength, and the complex can be used as a synergistic flame retardant, so that the dosage of the MPP flame retardant can be reduced, the technical problem that the mechanical property of a base material is reduced due to the addition of the flame retardant into the base material is solved, the residual carbon content can be increased during combustion, and the flame retardant effect is improved.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (6)
1. An irradiation crosslinking halogen-free low-smoke flame-retardant power cable is characterized by comprising the following raw materials in parts by weight: 55-70 parts of modified polyethylene, 30-35 parts of composite halogen-free flame retardant, 0.8-2 parts of ultraviolet absorbent, 1-5 parts of KH550 and 25-40 parts of polyolefin elastomer;
the irradiation crosslinking halogen-free low-smoke flame-retardant power cable is prepared by the following method:
firstly, adding modified polyethylene, a composite halogen-free flame retardant, a polyolefin elastomer, an ultraviolet absorbent and KH550 into an internal mixer, uniformly mixing, and taking out after internal mixing is finished to prepare a cable material;
and secondly, melting, plasticizing and extruding the cable material through an extruder, performing water cooling and granulation, extruding the material through the extruder again, wrapping the material on the surface of the conductor, and irradiating the conductor in an ultraviolet irradiation machine after traction, cooling, sizing and coiling, wherein the irradiation energy is controlled to be 5-15Mrad, so that the irradiation crosslinking halogen-free low-smoke flame-retardant power cable is prepared.
2. The irradiation crosslinked halogen-free low-smoke flame-retardant power cable according to claim 1, wherein the ultraviolet absorber is 2-hydroxy-4-n-octyloxybenzophenone.
3. The irradiation crosslinked halogen-free low-smoke flame-retardant power cable according to claim 1, characterized in that the composite halogen-free flame retardant is prepared by the following method:
step S1, adding salicylaldehyde into a sodium hydroxide aqueous solution with the mass fraction of 10%, uniformly stirring for 15min, transferring to a three-neck flask, heating in a water bath at 35-40 ℃, magnetically stirring for 20min, then dropwise adding a hydrogen peroxide aqueous solution with the mass fraction of 30%, controlling the dropwise adding time to be 30-45min, then heating to 45-50 ℃, continuing stirring for 10min, centrifuging, filtering, transferring to an oven with the temperature of 85-90 ℃ for drying for 4-5h, preparing a material A, and controlling the amount ratio of salicylaldehyde to sodium hydroxide to hydrogen peroxide to be 1: 0.5: 1;
step S2, uniformly mixing methanol and deionized water according to a weight ratio of 1: 10 to prepare a mixed solvent, adding the material A into one half of the mixed solvent, magnetically stirring for 10min to prepare a mixed solution B, adding cobalt acetate into the other half of the mixed solvent, uniformly stirring to prepare a solution C, dropwise adding the solution C into the mixed solution B, controlling the dropwise adding time to be 30min, refluxing, condensing and stirring for 10min at 70 ℃ to prepare a complex, filtering, and drying in an oven at 90 ℃ for 4-5 h;
and step S3, mixing the dried complex with MPP according to the weight ratio of 1: 1 to prepare the composite halogen-free flame retardant.
4. The irradiation crosslinked halogen-free low-smoke flame-retardant power cable according to claim 3, wherein the weight ratio of the material A, the cobalt acetate and the mixed solvent in step S2 is controlled to be 1: 10: 0.2-0.3.
5. The irradiation crosslinked halogen-free low-smoke flame-retardant power cable according to claim 1, wherein the modified polyethylene is prepared by the following method:
vacuum drying low-density polyethylene resin for 4-5h, controlling the vacuum degree at-0.10 MPa and the temperature at 60-70 ℃, then grinding and crushing an antioxidant, sieving with a 200-mesh sieve, mixing the dried low-density polyethylene resin with the crushed antioxidant, magnetically stirring for 30-45min, adding clove essential oil, continuously stirring for 10-15min, then blending, extruding and granulating through a double-screw extruder to obtain modified polyethylene, and controlling the weight ratio of the low-density polyethylene resin to the antioxidant to the clove essential oil to be 10: 0.1: 0.05.
6. The radiation crosslinked halogen-free low-smoke flame-retardant power cable according to claim 5, wherein the antioxidant is one or two of antioxidant 1010 and antioxidant 168 mixed in any proportion.
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