CN114864195B - Novel halogen-free low-smoke flame-retardant photovoltaic cable manufacturing method - Google Patents
Novel halogen-free low-smoke flame-retardant photovoltaic cable manufacturing method Download PDFInfo
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- CN114864195B CN114864195B CN202210706435.2A CN202210706435A CN114864195B CN 114864195 B CN114864195 B CN 114864195B CN 202210706435 A CN202210706435 A CN 202210706435A CN 114864195 B CN114864195 B CN 114864195B
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- 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 37
- 239000003063 flame retardant Substances 0.000 title claims abstract description 37
- 239000000779 smoke Substances 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 54
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- 229910021389 graphene Inorganic materials 0.000 claims abstract description 31
- 238000002156 mixing Methods 0.000 claims abstract description 16
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- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000005303 weighing Methods 0.000 claims abstract description 6
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- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 18
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- 238000003756 stirring Methods 0.000 claims description 16
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 claims description 15
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- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 7
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000006229 carbon black Substances 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 6
- 235000021355 Stearic acid Nutrition 0.000 claims description 6
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 6
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 6
- 239000008117 stearic acid Substances 0.000 claims description 6
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 5
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- 235000019441 ethanol Nutrition 0.000 claims description 4
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- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 claims description 2
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- 239000007788 liquid Substances 0.000 claims 1
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- 230000032683 aging Effects 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
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- 238000005054 agglomeration Methods 0.000 description 1
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- 125000000217 alkyl group Chemical group 0.000 description 1
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- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
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- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
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- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000012757 flame retardant agent Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
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- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
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- 229920003023 plastic Polymers 0.000 description 1
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- 238000006116 polymerization reaction Methods 0.000 description 1
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- 238000003860 storage Methods 0.000 description 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
Classifications
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- 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
- H01B13/26—Sheathing; Armouring; Screening; Applying other protective layers by winding, braiding or longitudinal lapping
- H01B13/2613—Sheathing; Armouring; Screening; Applying other protective layers by winding, braiding or longitudinal lapping by longitudinal lapping
- H01B13/2633—Bending and welding of a metallic screen
- H01B13/264—Details of the welding stage
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
-
- 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
- H01B13/10—Insulating conductors or cables by longitudinal lapping
-
- 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
- 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
- H01B3/28—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances natural or synthetic rubbers
-
- 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
-
- 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
- H01B7/28—Protection against damage caused by moisture, corrosion, chemical attack or weather
- H01B7/2806—Protection against damage caused by corrosion
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A30/00—Adapting or protecting infrastructure or their operation
- Y02A30/14—Extreme weather resilient electric power supply systems, e.g. strengthening power lines or underground power cables
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Abstract
The invention discloses a novel halogen-free low-smoke flame-retardant photovoltaic cable manufacturing method, which belongs to the technical field of cables and comprises the following steps: weighing ethylene propylene diene monomer, low-density polyethylene resin, modified graphene oxide, an accelerator, a reinforcing agent and dicumyl peroxide according to the mass ratio, and carrying out melt blending and plate vulcanization to obtain a rubber material; after the insulating layer is coated on the surface of the cable core, the rubber material is extruded and coated on the surface of the insulating layer to form an outer sheath layer, and the cable core is formed, air-cooled and rolled. According to the invention, ethylene propylene diene monomer and low-density polyethylene resin are used as base materials in the outer sheath layer of the photovoltaic cable, and modified graphene oxide is added into the base materials, so that the graphene oxide can be uniformly dispersed in the base materials after modification, and the flame retardant performance of the sheath material can be improved from the aspects of layered blocking, gas phase flame retardance and the like, so that the halogen-free low-smoke flame retardant photovoltaic cable is obtained, and the applicability and the use safety performance of the photovoltaic cable can be improved.
Description
Technical Field
The invention belongs to the technical field of cables, and particularly relates to a novel halogen-free low-smoke flame-retardant photovoltaic cable manufacturing method.
Background
The conductor part of the photovoltaic cable, namely the photovoltaic special cable, is a copper conductor or a tin-plated copper conductor, and the insulating layer is an irradiation crosslinking polyolefin insulation. A large number of direct current cables in the photovoltaic power station need to be laid outdoors. Because photovoltaic cables are often used under severe environmental conditions, such as high and low temperatures, intense ultraviolet radiation, high ozone concentrations, chemical corrosion, and the like, in some places, the on-site temperature of solar energy systems can be as high as 100 ℃ in sunny days. If the cable material is not required, the cable is fragile, even the cable sheath layer is decomposed, all the conditions directly increase the loss of the cable system, the risk of short circuit of the cable is increased, and the possibility of fire or personnel injury is higher in the long term, so that the photovoltaic cable for the solar energy system is required to use high-performance materials. At present, halogen-free requirements are set on a solar photovoltaic cable, the service life of the solar photovoltaic cable at 120 ℃ is required to reach more than 25 years, and meanwhile, the solar photovoltaic cable also has the performances of low temperature resistance, ozone resistance, weather resistance, direct current voltage resistance, dynamic penetration resistance, flame retardance and the like.
The prior art is shown in Chinese patent application (publication No. CN 101286377A) and is an irradiation crosslinking low-smoke halogen-free flame-retardant polyolefin cable material, which consists of the following components in percentage by mass: ethylene-vinyl acetate copolymer: 30-50%, high density polyethylene: 0-20%, magnesium hydroxide: 30-60%, red phosphorus: 0-10% of coupling agent: 1 to 5 percent of cross-linking agent: 0.1 to 1.5 percent of compatilizer: 1-5 percent of antioxidant: 0.1 to 1.5% of a lubricant: 0.1 to 1.5 percent. The irradiation crosslinking low-smoke halogen-free flame-retardant polyolefin cable material overcomes the harm of the traditional halogen flame retardant flame-retardant polyolefin material to the environment and the human body, and has the characteristics of no toxicity, green and environment protection. However, the flame-retardant effect is achieved through magnesium hydroxide, the magnesium hydroxide is used as an inorganic filler, the compatibility of the magnesium hydroxide and a polyethylene matrix is poor, and uniform dispersion is difficult to achieve, so that the flame-retardant effect is limited in improving effect, and further improvement and innovation are required.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a novel halogen-free low-smoke flame-retardant photovoltaic cable manufacturing method.
According to the invention, ethylene propylene diene monomer and low-density polyethylene resin are used as base materials in the outer sheath layer of the photovoltaic cable, and modified graphene oxide is added into the base materials, so that the graphene oxide can be uniformly dispersed in the base materials after modification, and the flame retardant performance of the sheath material can be improved from the aspects of layered blocking, gas phase flame retardance and the like, so that the halogen-free low-smoke flame retardant photovoltaic cable is obtained, and the applicability and the use safety performance of the photovoltaic cable can be improved.
The aim of the invention can be achieved by the following technical scheme:
the novel halogen-free low-smoke flame-retardant photovoltaic cable comprises a cable core, an insulating layer and an outer sheath layer, wherein the outer sheath layer comprises the following raw materials in parts by weight: 60-70 parts of ethylene propylene diene monomer, 25-30 parts of low-density polyethylene resin, 2-3 parts of modified graphene oxide, 4-5 parts of accelerator, 0.9-1.1 parts of reinforcing agent and 0.5-0.6 part of dicumyl peroxide;
the accelerator comprises ZnO, stearic acid and triallyl isocyanurate, and the mass ratio of the ZnO to the stearic acid to the triallyl isocyanurate is 0.8:1:0.5;
the reinforcing agent is a mixture of nano white carbon black and benzimidazole according to the mass ratio of 1:1;
the manufacturing method of the photovoltaic cable specifically comprises the following steps:
weighing ethylene propylene diene monomer, low-density polyethylene resin, modified graphene oxide, an accelerator, a reinforcing agent and dicumyl peroxide according to mass ratio, uniformly mixing, adding into a torque rheometer, melting and mixing at 100 ℃, wherein the screw speed is 60r/min, blending time is 25-30min, placing into a flat vulcanizing machine, preheating at 170 ℃ for 8min, maintaining pressure for 10min, repeating the exhaust process for 3 times, and finally cold pressing for 5min to obtain a rubber material;
and after the insulating layer is coated on the surface of the cable core, extruding and coating the rubber material on the surface of the insulating layer to form an outer sheath layer, and finally, forming, air cooling and rolling to obtain the photovoltaic cable.
LDPE and nano white carbon black particles are introduced into the continuous phase EPDM by a melt blending method, so that the interfacial tension of two phases can be reduced, and the interfacial adhesion is improved to promote mutual dispersion under the action of shearing force; the interpenetration continuous phase exists between the molecular chain segments at the interface of the amorphous part of LDPE and the EPDM, so that the defect of crystallization formed by mutual interference between the matrix and the filler during crystallization can be repaired, and the breakdown strength of the composite material is increased.
Further, the modified graphene oxide is prepared by the following steps:
s1, adding graphene oxide into a three-neck flask filled with N, N-Dimethylformamide (DMF), mechanically stirring for 1h at room temperature, adding 6-hexenyl-1-methylamine into the system, continuously stirring for 1h, then adding EDC-HCl, transferring the mixed solution into a water bath at 60 ℃ for continuous stirring, installing a reflux condensing device for reacting for 6h, washing the mixed solution obtained after the reaction with absolute ethyl alcohol for 4-5 times to remove 6-hexenyl-1-methylamine which does not participate in the reaction, and finally, drying the product in a vacuum drying oven at 50 ℃ for 12h to obtain an intermediate product 1; graphene oxide, N-dimethylformamide, 6-hexenyl-1-methylamine, EDC-HCl in an amount ratio of 0.2g to 100mL to 0.18g to 10mg;
the graphene oxide surface contains more oxygen-containing groups (-OH, epoxy groups and-COOH), and the-COOH reacts with-NH on 6-hexenyl-1-methylamine molecule under the action of EDC-HCl (carbonyl activating reagent) 2 The condensation reaction is carried out to obtain an intermediate product 1, wherein the intermediate product 1 is graphene oxide with a hexene chain bonded on the surface through-CO-NH-and double bonds introduced on the surface lay reaction sites for subsequent reactions; the reaction process of the step is as follows:
s2, placing the intermediate product 1 and N, N-Dimethylformamide (DMF) into a three-neck flask, performing ultrasonic dispersion for 3 hours at 38-40 ℃, adding a formic acid aqueous solution (mass fraction of 20%), cooling to room temperature, and then adding H 2 O 2 Water-solubleThe solution (30% by mass) is reacted at room temperature under stirring at a constant speed of 350r/min for 12H, suction-filtered, and repeatedly washed with distilled water until the pH of the washing solution is 6.9-7 (to remove unreacted HCOOH and H) 2 O 2 ) Drying the product in a vacuum drying oven at 50 ℃ for 12 hours to obtain an intermediate product 2; intermediate 1, N-dimethylformamide, aqueous formic acid solution H 2 O 2 The ratio of the dosage of the aqueous solution is 0.5g to 300mL to 100mL to 40mL;
under the action of HCOOH, double bonds on molecules of the intermediate product 1 are oxidized into epoxy groups under the action of hydrogen peroxide, so that an intermediate product 2 is obtained, and the specific reaction process is shown as follows;
s3, adding the intermediate product 2 and N, N-dimethylformamide into a three-neck flask, performing ultrasonic dispersion for 3 hours at 38-40 ℃, adding DOPO powder, continuing ultrasonic treatment for 1 hour, heating, reacting for 12 hours at 500r/min and 120 ℃, performing suction filtration, repeatedly washing with ethanol and distilled water for 3-4 times respectively to remove substances which do not participate in the reaction, and finally, drying the product in a vacuum drying oven at 50 ℃ for 12 hours to obtain modified graphene oxide; the dosage ratio of the intermediate 2 to the N, N-dimethylformamide to the DOPO powder is 0.5g to 300mL to 0.2g;
epoxy groups on the intermediate product 2 molecules and P-H on DOPO molecules are subjected to chemical reaction, so that the DOPO molecules are grafted on the surface of the graphene oxide, and modified graphene oxide is obtained; the specific reaction process is as follows:
the graphene oxide is modified, alkyl chains and DOPO molecules are grafted on the surface through chemical bonding, on one hand, partial oxygen-containing groups on the surface are consumed through chemical grafting modification, and organic chain groups are grafted, so that the hydrophilic performance of the graphene oxide surface and the agglomeration phenomenon among the graphene oxides are improved, and the uniform dispersion of the graphene oxide lamellar structure in the sheath base material is promoted; on the other hand, after graphene oxide is grafted by 6-hexenyl-1-methylamine, carbon-carbon double bonds are introduced into the surface, in the subsequent modification process, carbon-carbon double bonds which do not participate in subsequent reaction exist, and the carbon-carbon double bonds participate in the melt polymerization process of sheath base materials (low density polyethylene resin and ethylene propylene diene monomer), so that the acting force of the graphene oxide and the sheath base materials is further enhanced, the interface phenomenon is improved, and the modified graphene oxide is uniformly dispersed in the polymer base materials; DOPO molecules grafted on the surface of the graphene oxide are also uniformly dispersed in the sheath base material along with the graphene oxide;
the lamellar structure of the graphene oxide has good adsorptivity and barrier function, can effectively play the flame retardant effect of the lamellar structure, and the barrier property of the lamellar structure of the graphene oxide can reduce the transportation speed of corrosion-resistant particles so as to achieve the corrosion-resistant effect.
The invention has the beneficial effects that:
according to the invention, LDPE and nano white carbon black particles are introduced into the continuous phase EPDM by a melt blending method, so that the interfacial tension of two phases can be reduced, and the interfacial adhesion is improved to promote mutual dispersion under the action of shearing force; the interpenetration continuous phase exists between the molecular chain segments at the interface of the amorphous part of LDPE and the EPDM, so that the crystallization defect formed by the mutual interference between the matrix and the filler during crystallization can be repaired, and the breakdown strength of the sheath material is increased;
according to the invention, the modified graphene oxide is added into the sheath material, after being modified, the graphene oxide can be uniformly dispersed in the polymer matrix, the lamellar structure of the graphene oxide has good adsorptivity and barrier function, the flame retardant effect of the lamellar structure can be effectively exerted, the barrier property of the lamellar structure of the graphene oxide can reduce the transportation speed of corrosion-resistant particles, and further the corrosion resistance effect is achieved, in addition, DOPO molecules grafted on the surface of the graphene oxide are halogen-free flame retardant agents, and are uniformly dispersed in the sheath base material along with the graphene, so that the flame retardant performance is better exerted, the synergistic flame retardant effect is achieved with the graphene oxide, the lamellar barrier flame retardant effect is exerted, the gas-phase flame retardant effect is exerted by the DOPO, the flame retardant effect is exerted from multiple aspects, and the DOPO can be distributed in the base material through the actions of the graphene oxide and the base material, and the migration phenomenon in the storage process can be effectively avoided;
according to the invention, the halogen-free low-smoke flame retardance of the cable sheath material can be realized from multiple aspects, so that the outer sheath layer has the halogen-free low-smoke high flame retardance, the halogen-free low-smoke flame retardance type photovoltaic cable is obtained, and the applicability and the use safety performance of the photovoltaic cable can be improved.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Preparing modified graphene oxide:
s1, adding 0.6g of graphene oxide into a three-neck flask filled with 300mL of N, N-Dimethylformamide (DMF), mechanically stirring for 1h at room temperature, adding 0.54g of 6-hexenyl-1-methylamine into the system, continuously stirring for 1h, then adding 30mg of EDC-HCl, transferring the mixed solution into a water bath at 60 ℃ for continuous stirring, installing a reflux condensing device for reacting for 6h, washing the mixed solution obtained after the reaction with absolute ethyl alcohol for 4 times to remove the 6-hexenyl-1-methylamine which does not participate in the reaction, and finally, drying the product in a vacuum drying box at 50 ℃ for 12h to obtain an intermediate product 1;
s2, putting 0.5g of intermediate 1 and 300mL of N, N-Dimethylformamide (DMF) into a three-neck flask, performing ultrasonic dispersion for 3H at 38 ℃, adding 100mL of aqueous solution of formic acid (mass fraction 20%), cooling to room temperature, and then adding 40mL of H 2 O 2 The aqueous solution (30% by mass) was reacted at room temperature under constant stirring at 350r/min for 12H, suction filtered and repeatedly washed with distilled water until the pH of the wash solution was 6.9 (to remove unreacted HCOOH and H) 2 O 2 ) Drying the product in a vacuum drying oven at 50 ℃ for 12 hours to obtain an intermediate product 2;
s3, adding 0.5g of intermediate 2 and 300mL of N, N-dimethylformamide into a three-neck flask, performing ultrasonic dispersion for 3 hours at 38 ℃, adding 0.2g of DOPO powder, continuing ultrasonic treatment for 1 hour, heating, reacting for 12 hours at 500r/min and 120 ℃, performing suction filtration, repeatedly washing with ethanol and distilled water for 3 times respectively, removing substances which do not participate in the reaction, and finally drying the product in a vacuum drying oven at 50 ℃ for 12 hours to obtain the modified graphene oxide.
Example 2
Preparing modified graphene oxide:
s1, adding 0.6g of graphene oxide into a three-neck flask filled with 300mL of N, N-Dimethylformamide (DMF), mechanically stirring for 1h at room temperature, adding 0.54g of 6-hexenyl-1-methylamine into the system, continuously stirring for 1h, then adding 30mg of EDC-HCl, transferring the mixed solution into a water bath at 60 ℃ for continuous stirring, installing a reflux condensing device for reacting for 6h, washing the mixed solution obtained after the reaction with absolute ethyl alcohol for 5 times to remove the 6-hexenyl-1-methylamine which does not participate in the reaction, and finally, drying the product in a vacuum drying box at 50 ℃ for 12h to obtain an intermediate product 1;
s2, putting 0.5g of intermediate 1 and 300mL of N, N-Dimethylformamide (DMF) into a three-neck flask, performing ultrasonic dispersion for 3H at 40 ℃, adding 100mL of aqueous solution of formic acid (mass fraction 20%), cooling to room temperature, and then adding 40mL of H 2 O 2 The aqueous solution (30% by mass) was reacted at room temperature under constant stirring at 350r/min for 12h, suction filtered, and repeatedly washed with distilled water until the pH of the wash solution was 7 (to removeUnreacted HCOOH and H 2 O 2 ) Drying the product in a vacuum drying oven at 50 ℃ for 12 hours to obtain an intermediate product 2;
s3, adding 0.5g of intermediate 2 and 300mL of N, N-dimethylformamide into a three-neck flask, performing ultrasonic dispersion for 3h at 40 ℃, adding 0.2g of DOPO powder, continuing ultrasonic treatment for 1h, heating, reacting for 12h at 500r/min and 120 ℃, performing suction filtration, repeatedly washing with ethanol and distilled water for 4 times respectively to remove substances which do not participate in the reaction, and finally drying the product in a vacuum drying oven at 50 ℃ for 12h to obtain the modified graphene oxide.
Example 3
Preparing a novel halogen-free low-smoke flame-retardant photovoltaic cable, wherein the cable comprises a cable core, an insulating layer and an outer sheath layer;
the manufacturing method of the photovoltaic cable specifically comprises the following steps:
weighing 60g of ethylene propylene diene monomer, 25g of low-density polyethylene resin, 2g of modified graphene oxide prepared in example 1, 4g of accelerator, 0.9g of reinforcing agent and 0.5g of dicumyl peroxide, uniformly mixing, adding into a torque rheometer, melting and mixing at 100 ℃, the screw speed of 60r/min, blending for 25min, then placing into a flat vulcanizing machine, preheating at 170 ℃ for 8min, maintaining pressure for 10min, repeating the exhaust process for 3 times, and finally cold pressing for 5min to obtain rubber materials;
after the surface of the cable core is coated with the insulating layer, extruding and coating the rubber material on the surface of the insulating layer to form an outer sheath layer, and finally, forming, air cooling and rolling to obtain the photovoltaic cable;
the accelerator comprises ZnO, stearic acid and triallyl isocyanurate in a mass ratio of 0.8:1:0.5;
the reinforcing agent is a mixture of nano white carbon black and benzimidazole according to a mass ratio of 1:1.
Example 4
Preparing a novel halogen-free low-smoke flame-retardant photovoltaic cable, wherein the cable comprises a cable core, an insulating layer and an outer sheath layer;
the manufacturing method of the photovoltaic cable specifically comprises the following steps:
weighing 65g of ethylene propylene diene monomer, 28g of low-density polyethylene resin, 2.5g of modified graphene oxide prepared in example 2, 4.5g of accelerator, 1.0g of reinforcing agent and 0.55g of dicumyl peroxide, uniformly mixing, adding into a torque rheometer, melting and mixing at 100 ℃, rotating a screw at 60r/min for 28min, preheating in a flat vulcanizing machine at 170 ℃ for 8min, maintaining pressure for 10min, repeating the exhaust process for 3 times, and finally cold pressing for 5min to obtain a rubber material;
after the surface of the cable core is coated with the insulating layer, extruding and coating the rubber material on the surface of the insulating layer to form an outer sheath layer, and finally, forming, air cooling and rolling to obtain the photovoltaic cable;
the accelerator comprises ZnO, stearic acid and triallyl isocyanurate in a mass ratio of 0.8:1:0.5;
the reinforcing agent is a mixture of nano white carbon black and benzimidazole according to a mass ratio of 1:1.
Example 5
Preparing a novel halogen-free low-smoke flame-retardant photovoltaic cable, wherein the cable comprises a cable core, an insulating layer and an outer sheath layer;
the manufacturing method of the photovoltaic cable specifically comprises the following steps:
weighing 70g of ethylene propylene diene monomer, 30g of low-density polyethylene resin, 3g of modified graphene oxide, 5g of accelerator, 1.1g of reinforcing agent and 0.6g of dicumyl peroxide, uniformly mixing, adding into a torque rheometer, melting and mixing at 100 ℃ for 30min at a screw speed of 60r/min, placing into a flat vulcanizing machine, preheating at 170 ℃ for 8min, maintaining pressure for 10min, repeating the exhaust process for 3 times, and finally cold pressing for 5min to obtain a rubber material;
after the surface of the cable core is coated with the insulating layer, extruding and coating the rubber material on the surface of the insulating layer to form an outer sheath layer, and finally, forming, air cooling and rolling to obtain the photovoltaic cable;
the accelerator comprises ZnO, stearic acid and triallyl isocyanurate in a mass ratio of 0.8:1:0.5;
the reinforcing agent is a mixture of nano white carbon black and benzimidazole according to a mass ratio of 1:1.
Comparative example 1
The modified graphene oxide in example 3 is changed into common graphene oxide, and the rest raw materials and the preparation process are unchanged.
Comparative example 2
The modified graphene oxide in example 3 was changed to DOPO powder, and the remaining raw materials and preparation process were unchanged.
The following performance tests were carried out on the rubber compounds and cables obtained in examples 3 to 5 and comparative examples 1 to 2:
mechanical properties: testing tensile strength and elongation at break of the cable according to GB/T2951 general test method for insulation and sheath materials of wires and cables;
aging performance: according to GB/T2951 general test method for insulation and sheath materials of wires and cables, testing the retention rate of elongation at break after 185 ℃/120h air box heat aging;
combustion performance: the combustion performance test is carried out on the material of the outer sheath layer of the cable by referring to 6.3 wire and cable sleeve plastic materials in GB 8624-1997 'method for classifying combustion performance of building materials', and the oxygen index and the combustion performance level of the outer sheath layer are tested;
the results are shown in the following table:
from the above table data, the tensile strength of the cables prepared in examples 3 to 5 was 9.8MPa and above, the elongation at break was 248% or above, which indicates that the cables prepared in the invention had satisfactory mechanical properties, and the elongation at break retention after 185 ℃/120h air box heat aging was 59.2% or above, which indicates that the cables prepared in the invention had satisfactory aging resistance; the oxygen index is 30.2% or above, and the flame retardant has B2-grade combustion performance, which shows that the flame retardant has higher flame retardant property; as can be seen from the data of the combination comparative examples 1 and 2, the graphene oxide can be uniformly dispersed in the sheath base material after modification, the mechanical properties of the base material are not affected, and the graphene oxide and the DOPO can generate a synergistic effect after being combined through chemical bonding, so that the improvement of the flame retardant effect is commonly promoted.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, 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 present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. 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 merely illustrative and explanatory of the invention, as various modifications and additions may be made to the particular embodiments described, or in a similar manner, by those skilled in the art, without departing from the scope of the invention or exceeding the scope of the invention as defined in the claims.
Claims (7)
1. The novel halogen-free low-smoke flame-retardant photovoltaic cable manufacturing method is characterized in that the photovoltaic cable comprises a cable core, an insulating layer and an outer sheath layer, and the outer sheath layer comprises the following raw materials in parts by weight: 60-70 parts of ethylene propylene diene monomer, 25-30 parts of low-density polyethylene resin, 2-3 parts of modified graphene oxide, 4-5 parts of accelerator, 0.9-1.1 parts of reinforcing agent and 0.5-0.6 part of dicumyl peroxide;
the manufacturing method of the photovoltaic cable specifically comprises the following steps:
weighing ethylene propylene diene monomer, low-density polyethylene resin, modified graphene oxide, an accelerator, a reinforcing agent and dicumyl peroxide according to mass ratio, uniformly mixing, adding into a torque rheometer, melting and mixing at 100 ℃, wherein the screw speed is 60r/min, blending time is 25-30min, placing into a flat vulcanizing machine, preheating at 170 ℃ for 8min, maintaining pressure for 10min, repeating the exhaust process for 3 times, and finally cold pressing for 5min to obtain a rubber material;
after the surface of the cable core is coated with the insulating layer, extruding and coating the rubber material on the surface of the insulating layer to form an outer sheath layer, and finally, forming, air cooling and rolling to obtain the photovoltaic cable;
wherein the modified graphene oxide is prepared by the following steps:
s1, adding graphene oxide into a three-neck flask filled with N, N-dimethylformamide, mechanically stirring for 1h at room temperature, adding 6-hexenyl-1-methylamine into the system, continuously stirring for 1h, then adding EDC-HCl, transferring the mixed solution into a water bath at 60 ℃ for continuous stirring, installing a reflux condensing device for reacting for 6h, washing the mixed solution obtained after the reaction with absolute ethyl alcohol for 4-5 times to remove 6-hexenyl-1-methylamine which does not participate in the reaction, and finally, drying the product in a vacuum drying oven at 50 ℃ for 12h to obtain an intermediate product 1;
s2, placing the intermediate product 1 and N, N-dimethylformamide into a three-neck flask, performing ultrasonic dispersion for 3 hours at 38-40 ℃, adding a formic acid aqueous solution, cooling to room temperature, and then adding H 2 O 2 Reacting the aqueous solution for 12 hours at room temperature under the condition of 350r/min constant stirring, filtering, repeatedly washing with distilled water until the pH value of the washing liquid is 6.9-7, and drying the product in a vacuum drying oven at 50 ℃ for 12 hours to obtain an intermediate product 2;
s3, adding the intermediate product 2 and N, N-dimethylformamide into a three-neck flask, performing ultrasonic dispersion for 3 hours at 38-40 ℃, adding DOPO powder, continuing ultrasonic treatment for 1 hour, heating, reacting for 12 hours at 500r/min and 120 ℃, performing suction filtration, repeatedly washing with ethanol and distilled water for 3-4 times respectively, removing substances which do not participate in the reaction, and finally, drying the product in a vacuum drying oven at 50 ℃ for 12 hours to obtain the modified graphene oxide.
2. The method for manufacturing the novel halogen-free low-smoke flame-retardant photovoltaic cable according to claim 1, wherein the accelerator comprises ZnO, stearic acid and triallyl isocyanurate in a mass ratio of 0.8:1:0.5.
3. The method for manufacturing the novel halogen-free low-smoke flame-retardant photovoltaic cable according to claim 1, wherein the reinforcing agent is a mixture of nano white carbon black and benzimidazole according to a mass ratio of 1:1.
4. The method for manufacturing the novel halogen-free low-smoke flame-retardant photovoltaic cable according to claim 1, wherein the dosage ratio of graphene oxide, N-dimethylformamide, 6-hexenyl-1-methylamine and EDC-HCl in the step S1 is 0.2g:100mL:0.18g:10mg.
5. The method for manufacturing the novel halogen-free low-smoke flame-retardant photovoltaic cable according to claim 1, wherein in the step S2, the intermediate product 1, N-dimethylformamide, formic acid aqueous solution and H are adopted 2 O 2 The ratio of the amounts of aqueous solutions was 0.5 g/300 mL/100 mL/40 mL.
6. The method for manufacturing the novel halogen-free low-smoke flame-retardant photovoltaic cable according to claim 5, wherein the mass fraction of the formic acid aqueous solution is 20%, H 2 O 2 The mass fraction of the aqueous solution was 30%.
7. The method for manufacturing the novel halogen-free low-smoke flame-retardant photovoltaic cable according to claim 1, wherein the dosage ratio of the intermediate product 2, N-dimethylformamide and DOPO powder in the step S3 is 0.5g:300mL:0.2g.
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