CN111961274A - Insulating material for photovoltaic cable and preparation method thereof - Google Patents

Insulating material for photovoltaic cable and preparation method thereof Download PDF

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Publication number
CN111961274A
CN111961274A CN202010766683.7A CN202010766683A CN111961274A CN 111961274 A CN111961274 A CN 111961274A CN 202010766683 A CN202010766683 A CN 202010766683A CN 111961274 A CN111961274 A CN 111961274A
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ethylene
temperature
insulating material
zone
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邹存洋
徐静
陈静
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Far East New Materials Co ltd
New Far East Cable Co Ltd
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Far East New Materials Co ltd
New Far East Cable Co Ltd
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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
    • 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
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0853—Vinylacetate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • 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
    • 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
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0869—Acids or derivatives thereof
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general
    • 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
    • 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
    • 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
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/066—LDPE (radical process)

Abstract

The invention discloses an insulating material for a photovoltaic cable and a preparation method thereof, wherein the insulating material for the photovoltaic cable is prepared from the following raw materials in parts by mass: 10-30 parts of ethylene-vinyl acetate copolymer, 1-20 parts of ethylene butyl acrylate, 1-10 parts of ethylene propylene diene monomer, 5-20 parts of metallocene low-density polyethylene, 30-60 parts of modified aluminum hydroxide, 1-10 parts of diethyl aluminum phosphinate, 1-5 parts of compatilizer, 0.5-3 parts of crosslinking sensitizer, 0.5-2 parts of antioxidant and 1-5 parts of lubricant. The invention ensures that the material can meet the requirement of service life and has excellent insulating property, mechanical property and processing property.

Description

Insulating material for photovoltaic cable and preparation method thereof
Technical Field
The invention relates to the technical field of cables, in particular to an insulating material for a photovoltaic cable and a preparation method thereof.
Background
In the 21 st century, along with the concept of sustainable development, people are increasingly keen in various countries in the world, the scale of development and utilization of solar power generation, which is one of main clean energy, is rapidly enlarged, the technology is continuously improved, the cost is also obviously reduced, and a good development prospect is presented. In 2000-2016 years, the global accumulated installed capacity of the photovoltaic industry is increased from 1250MW to 304300MW, and the annual composite growth rate is as high as 40.98%.
The photovoltaic cable is used as a component part for connecting the photovoltaic module, and plays a particularly critical role in the normal operation of a photovoltaic power generation system. The insulating material of the photovoltaic cable is very important for the normal operation of the cable, and not only the insulating material for the photovoltaic cable is required to have excellent insulating property, but also the requirements on moisture and heat resistance, ozone resistance, flame retardance, smoke density, service life, low smoke, zero halogen and the like are also met.
At present, the standard of the photovoltaic cable is the most widely applied to IEC62930-2017, and in addition to the conventional performance requirements, the IEC62930-2017 provides great challenges for insulating materials for the photovoltaic cable according to the requirements on the service life of more than 25 years at 90 ℃ and the 1.8kV direct current withstand voltage of 85 ℃ for 10 days. Because finished cables have flame-retardant requirements, a conventional insulating material needs to be filled with a large amount of inorganic flame retardant to realize certain flame-retardant performance, however, the mechanical property of the material is seriously reduced and the processability is deteriorated due to the increase of the addition amount of the inorganic flame retardant, and meanwhile, the insulation resistance of the insulating material after being soaked in water is reduced and the insulating performance is deteriorated due to the hydrophilicity of the inorganic filler.
Disclosure of Invention
The invention aims to provide an insulating material for a photovoltaic cable and a preparation method thereof, which can ensure that the material can meet the requirement of service life and has excellent insulating property, mechanical property and processability.
The technical scheme for realizing the purpose of the invention is as follows:
an insulating material for a photovoltaic cable is composed of the following raw materials in parts by mass: 10-30 parts of ethylene-vinyl acetate copolymer, 1-20 parts of ethylene butyl acrylate, 1-10 parts of ethylene propylene diene monomer, 5-20 parts of metallocene low-density polyethylene, 30-60 parts of modified aluminum hydroxide, 1-10 parts of diethyl aluminum phosphinate, 1-5 parts of compatilizer, 0.5-3 parts of crosslinking sensitizer, 0.5-2 parts of antioxidant and 1-5 parts of lubricant.
Further, the content of vinyl acetate in the ethylene-vinyl acetate copolymer is 14-30%, and the melt index is (190 ℃, 2.16kg)2-6g/10 min.
Furthermore, the content of butyl acrylate in the ethylene butyl acrylate is 20-30%, and the melt index (190 ℃, 2.16kg) is 1-6g/10 min.
Further, the ethylene content of the ethylene-propylene-diene monomer rubber is 50-60%, the propylene content is 35-45%, and the third monomer is ethylidene-norbornene and has a content of 4-6%; the Mooney viscosity of the ethylene propylene diene monomer rubber is (ML 1+4,125 ℃) 60-90.
Further, the density of the metallocene low-density polyethylene is 0.91-0.925g/cm3The melt index is (190 ℃, 2.16kg)1-5g/10 min.
Further, the modified aluminum hydroxide is silane coupling agent surface modified aluminum hydroxide with the mesh number of 4000-8000 meshes.
Furthermore, the particle size D50 of the aluminum diethylphosphinate is less than or equal to 10 μm, and the decomposition temperature (TGA thermal weight loss is 1%): is > 320 ℃.
Further, the compatilizer is a maleic anhydride grafted polyolefin material, the base material is polyethylene, an ethylene octene copolymer or an ethylene-vinyl acetate copolymer, and the grafting rate is 0.5-2%.
Further, the crosslinking sensitizer is trimethylolpropane triacrylate, triallyl isocyanurate, or trimethylolpropane triacrylate.
Further, the antioxidant is one or more of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester, 4' -thiobis (6-tert-butyl-3-methylphenol), 2, 4-trimethyl-1, 2-dihydroquinoline polymer, dilauryl thiodipropionate and distearyl thiodipropionate.
Further, the lubricant is one or more of silicone master batch, stearic acid, zinc stearate, calcium stearate and polyethylene wax.
A preparation method of an insulating material for a photovoltaic cable is characterized by comprising the following steps:
the method comprises the following steps: weighing the components in parts by mass;
step two: the components are melted and blended through an internal mixer, the internal mixing temperature is 120-140 ℃, the internal mixing time is 5-15 minutes, and then the components are mixed through a reciprocating machine, wherein the reciprocating machine is divided into four zones, and the working temperature of each zone is as follows: the temperature of the first area is 90-100 ℃, the temperature of the second area is 170-180 ℃, the temperature of the third area is 150-160 ℃, and the temperature of the fourth area is 100-120 ℃;
step three: and (2) granulating the melted and blended materials after sequentially passing through the zones by adopting a single-screw extruder, wherein the single-screw extruder is divided into five zones, and the working temperature of each zone is as follows: the temperature of the first zone is 100-120 ℃, the temperature of the second zone is 110-120 ℃, the temperature of the third zone is 130-140 ℃, the temperature of the fourth zone is 140-160 ℃, and the temperature of the fifth zone is 150-160 ℃.
By adopting the technical scheme, the invention has the following beneficial effects:
(1) the invention realizes excellent insulating property, mechanical property and processing property under high filling of the material by reasonably matching the ethylene-vinyl acetate copolymer, the ethylene butyl acrylate, the ethylene propylene diene monomer and the metallocene low-density polyethylene and surface modification of the aluminum hydroxide inorganic flame retardant, the light transmittance in smoke can reach more than 90 percent, and simultaneously the invention can meet the insulating direct current voltage withstand test and low temperature resistance test of 1.8kV at 85 ℃ for 10 days; through the compounding of the antioxidant and the high-temperature resistance of the ethylene butyl acrylate, the material can pass the service life of more than 25 years at 90 ℃; the flame retardant effect of the material is further improved by adding diethyl aluminum phosphinate as a halogen-free flame retardant.
(2) The third monomer of the ethylene propylene diene monomer is ethylidene-norbornene, so that the material has better heat resistance.
(3) The modified aluminum hydroxide is the silane coupling agent surface modified aluminum hydroxide which is a common inorganic flame retardant, has low production cost, but has poor compatibility with organic high polymers, and can reduce the mechanical properties of the material.
(4) The compatilizer is maleic anhydride grafted polyolefin material, and by introducing strong polar reactive groups, the material has high polarity and reactivity, and the compatibility of the composite material and the dispersibility of the filler can be greatly improved, so that the mechanical strength of the composite material is improved, the compatibility of the inorganic filler and the organic resin is improved, the tensile strength and the impact strength of a product are improved, high filling is realized, the resin consumption is reduced, the processing rheological property is improved, and the surface smoothness is improved.
(5) The crosslinking sensitizer is trimethylolpropane triacrylate, triallyl isocyanurate or trimethylolpropane triacrylate, so that the heat resistance, solvent resistance, weather resistance, corrosion resistance and flame retardance of a crosslinking agent product can be obviously improved, and the mechanical property and the electrical property are improved.
(6) The cross-linking sensitizer antioxidant provided by the invention provides multiple choices, has a wide application range, can effectively prevent the material from aging, and prolongs the service life.
(7) According to the preparation method, through adjustment of the formula, the agglomeration time of the materials in the internal mixer can be shortened to be within 10 minutes, and then the materials are further quickly mixed and dispersed through a reciprocating machine, so that the production efficiency is improved, the conventional formula resin has a higher melting point and needs more time for agglomeration, the production efficiency is remarkably improved, the production cost is remarkably reduced, and 700kg/h can be achieved.
Detailed Description
In order to better understand the above technical solutions, the following detailed descriptions will be provided with reference to specific embodiments.
Comparative example 1
Comparative example 1 is a photovoltaic cable insulating material in the prior art, and comprises the following raw materials in parts by mass: 26 parts of ethylene-vinyl acetate copolymer, 15 parts of low-density polyethylene, 52 parts of silane coupling agent surface modified aluminum hydroxide, 1 part of compatilizer, 2 parts of crosslinking sensitizer, 0.5 part of antioxidant and 1.5 parts of lubricant.
Wherein the content of vinyl acetate in the ethylene-vinyl acetate copolymer is 14%, and the melt index (190 ℃, 2.16kg) is 2g/10 min; the density of the low-density polyethylene is 0.912g/cm3The melt index is (190 ℃, 2.16kg)2g/10 min; the mesh number of the silane coupling agent surface modified aluminum hydroxide is 8000 meshes; the compatilizer is maleic anhydride grafted polyolefin material, and the grafting rate is 1%; the crosslinking sensitizer is trimethylolpropane triacrylate; the antioxidant is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate]The weight ratio of the pentaerythritol ester to the 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer is 1: 1; the lubricant is silicone master batch, zinc stearate and polyethylene wax, and the weight ratio is 1:1: 1.
(example 1)
The insulating material for the photovoltaic cable in the embodiment 1 is prepared from the following raw materials in parts by mass: 15 parts of ethylene-vinyl acetate copolymer, 5 parts of ethylene butyl acrylate, 5 parts of ethylene propylene diene monomer, 12 parts of metallocene low-density polyethylene, 50 parts of silane coupling agent surface modified aluminum hydroxide, 5 parts of diethyl aluminum phosphinate, 2 parts of compatilizer, 0.5 part of crosslinking sensitizer, 1.5 parts of antioxidant and 4 parts of lubricant. The aluminum hydroxide is a common inorganic flame retardant, has low production cost, but has poor compatibility with organic high polymers, and can reduce the mechanical properties of the material.
Wherein the content of vinyl acetate in the ethylene-vinyl acetate copolymer is 26%, and the melt index (190 ℃, 2.16kg) is 6g/10 min; the content of butyl acrylate in the ethylene butyl acrylate is 28 percent, and the melt index is (190 ℃, 2.16kg)2g/10 min; the ethylene content of the ethylene-propylene-diene monomer is 50%, the propylene content is 45%, the third monomer is ethylidene-norbornene, the heat resistance of the material is better, the content is 5%, and the Mooney viscosity of the ethylene-propylene-diene monomer is (ML 1+4,125 ℃) 80; the density of the metallocene low-density polyethylene is 0.912g/cm3The melt index is (190 ℃, 2.16kg)2g/10 min; the mesh number of the silane coupling agent surface modified aluminum hydroxide is 8000 meshes; the grain diameter D50 of the aluminum diethylphosphinate is less than or equal to 10 mu m, and the decomposition temperature (TGA thermal weight loss is 1%): is > 320 ℃.
The compatilizer is maleic anhydride grafted polyolefin material, and by introducing strong polar reactive groups, the material has high polarity and reactivity, and can greatly improve the compatibility of the composite material and the dispersibility of the filler, so that the mechanical strength of the composite material is improved, the compatibility of the inorganic filler and the organic resin is improved, the tensile strength and the impact strength of a product are improved, high filling is realized, the resin consumption is reduced, the processing rheological property is improved, the surface smoothness is improved, the base material is polyethylene, and the grafting ratio is 0.8%; the crosslinking sensitizer is trimethylolpropane triacrylate, so that the heat resistance, solvent resistance, weather resistance, corrosion resistance and flame retardance of a crosslinking agent product can be obviously improved, and the mechanical property and the electrical property are improved; the antioxidant is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester and thiodipropionic acid distearyl ester in the weight ratio of 2: 1. The lubricant is silicone master batch, polyethylene wax and stearic acid in a weight ratio of 2:1: 1.
The preparation method of the insulating material for photovoltaic cables of example 1 includes the steps of:
the method comprises the following steps: weighing the components in parts by mass;
step two: the components are melted and blended by an internal mixer, the internal mixing temperature is 130 ℃, the internal mixing time is 10 minutes, then the components are mixed by a reciprocating machine, the reciprocating machine is divided into four areas, and the working temperature of each area is as follows: a first zone of 95 ℃, a second zone of 175 ℃, a third zone of 155 ℃, a fourth zone of 110 ℃;
step three: granulating after the melted and blended materials sequentially pass through each zone by adopting a single-screw extruder, wherein the single-screw extruder is divided into five zones, and the working temperature of each zone is as follows: the first zone is 110 ℃, the second zone is 120 ℃, the third zone is 130 ℃, the fourth zone is 150 ℃ and the fifth zone is 150 ℃.
Through the adjustment of the formula, the conglomeration time of the materials in the internal mixer can be shortened to within 10 minutes, and then the materials are further quickly mixed and dispersed through a reciprocating machine, so that the production efficiency is improved, the conventional formula resin has higher melting point and needs more time for conglomeration, the production efficiency is obviously improved, the production cost is obviously reduced, and the conglomeration time can reach 700 kg/h.
(example 2)
The insulating material for the photovoltaic cable in embodiment 2 is composed of the following raw materials in parts by mass: 20 parts of ethylene-vinyl acetate copolymer, 3 parts of ethylene butyl acrylate, 7 parts of ethylene propylene diene monomer, 7 parts of metallocene low-density polyethylene, 50 parts of silane coupling agent surface modified aluminum hydroxide, 3 parts of diethyl aluminum phosphinate, 3 parts of compatilizer, 1 part of crosslinking sensitizer, 2 parts of antioxidant and 4 parts of lubricant.
Wherein the content of vinyl acetate in the ethylene-vinyl acetate copolymer is 28%, and the melt index (190 ℃, 2.16kg) is 5g/10 min; the content of butyl acrylate in the ethylene butyl acrylate is 28 percent, and the melt index is (190 ℃, 2.16kg)2g/10 min; the ethylene content of the ethylene-propylene-diene monomer is 55%, the propylene content is 40%, the third monomer is ethylidene-norbornene, the heat resistance of the material is better, the content is 5%, and the Mooney viscosity of the ethylene-propylene-diene monomer is (ML 1+4,125 ℃) 80; the density of the metallocene low-density polyethylene is 0.912g/cm3The melt index is (190 ℃, 2.16kg)2g/10 min; the mesh number of the silane coupling agent surface modified aluminum hydroxide is 8000 meshes; granules of aluminum diethylphosphinateThe diameter D50 is less than or equal to 10 μm, and the decomposition temperature (TGA thermal weight loss 1%): is > 320 ℃.
The compatilizer is maleic anhydride grafted polyolefin material, the base material is ethylene-octene copolymer, and the grafting rate is 1%; the crosslinking sensitizer is trimethylolpropane triacrylate; the antioxidant is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester, 2, 4-trimethyl-1, 2-dihydroquinoline polymer and dilauryl thiodipropionate, and the weight ratio is 2:1: 1; the lubricant is silicone master batch, zinc stearate and polyethylene wax, and the weight ratio is 1.5:1.5: 1.
The preparation method of the insulating material for photovoltaic cables of example 2 is the same as that of example 1.
(example 3)
The insulating material for the photovoltaic cable in embodiment 3 is composed of the following raw materials in parts by mass: 18 parts of ethylene-vinyl acetate copolymer, 4 parts of ethylene butyl acrylate, 5 parts of ethylene propylene diene monomer, 10 parts of metallocene low-density polyethylene, 52 parts of silane coupling agent surface modified aluminum hydroxide, 2 parts of diethyl aluminum phosphinate, 2.5 parts of compatilizer, 1 part of crosslinking sensitizer, 1.5 parts of antioxidant and 4 parts of lubricant.
Wherein the content of vinyl acetate in the ethylene-vinyl acetate copolymer is 28%, and the melt index (190 ℃, 2.16kg) is 6g/10 min; the content of butyl acrylate in the ethylene butyl acrylate is 28 percent, and the melt index is (190 ℃, 2.16kg)2g/10 min; the ethylene content of the ethylene-propylene-diene monomer is 55%, the propylene content is 40%, the third monomer is ethylidene-norbornene, the heat resistance of the material is better, the content is 5%, and the Mooney viscosity of the ethylene-propylene-diene monomer is (ML 1+4,125 ℃) 80; the density of the metallocene low-density polyethylene is 0.912g/cm3, and the melt index is (190 ℃, 2.16kg)2g/10 min; the mesh number of the silane coupling agent surface modified aluminum hydroxide is 8000 meshes; the grain diameter D50 of the aluminum diethylphosphinate is less than or equal to 10 mu m, and the decomposition temperature (TGA thermal weight loss is 1%): is > 320 ℃.
The compatilizer is maleic anhydride grafted polyolefin material, the base material is ethylene-vinyl acetate copolymer, and the grafting rate is 1%; the crosslinking sensitizer is trimethylolpropane triacrylate; the antioxidant is 4,4' -thiobis (6-tert-butyl-3-methylphenol), 2, 4-trimethyl-1, 2-dihydroquinoline polymer and dilauryl thiodipropionate in a weight ratio of 1:1: 1; the lubricant is silicone master batch, stearic acid and polyethylene wax in a weight ratio of 1:1: 2.
The preparation method of the insulating material for photovoltaic cables of example 3 is the same as that of example 1.
(example 4)
The insulating material for the photovoltaic cable in embodiment 4 is composed of the following raw materials in parts by mass: 10 parts of ethylene-vinyl acetate copolymer, 15 parts of ethylene butyl acrylate, 5 parts of ethylene propylene diene monomer, 15 parts of metallocene low-density polyethylene, 40 parts of silane coupling agent surface modified aluminum hydroxide, 10 parts of diethyl aluminum phosphinate, 1 part of compatilizer, 2 parts of crosslinking sensitizer, 0.5 part of antioxidant and 1.5 parts of lubricant.
Wherein the content of vinyl acetate in the ethylene-vinyl acetate copolymer is 14%, and the melt index (190 ℃, 2.16kg) is 2g/10 min; the content of butyl acrylate in the ethylene butyl acrylate is 20 percent, and the melt index is (190 ℃, 2.16kg)4g/10 min; the ethylene content of the ethylene-propylene-diene monomer is 60%, the propylene content is 36%, the third monomer is ethylidene-norbornene, the heat resistance of the material is better, the content is 4%, and the Mooney viscosity of the ethylene-propylene-diene monomer is (ML 1+4,125 ℃) 60; the density of the metallocene low density polyethylene is 0.918g/cm3The melt index is (190 ℃, 2.16kg)3g/10 min; the mesh number of the silane coupling agent surface modified aluminum hydroxide is 4000 meshes; the grain diameter D50 of the aluminum diethylphosphinate is less than or equal to 10 mu m, and the decomposition temperature (TGA thermal weight loss is 1%): is > 320 ℃.
The compatilizer is maleic anhydride grafted polyolefin material, the base material is ethylene-vinyl acetate copolymer, and the grafting rate is 1.5 percent; the crosslinking sensitizer is triallyl isocyanurate, so that the heat resistance, solvent resistance, weather resistance, corrosion resistance and flame retardance of a crosslinking agent product can be obviously improved, and the mechanical property and the electrical property are improved; the antioxidant is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester; the lubricant is silicone master batch.
The preparation method of the insulating material for photovoltaic cables of embodiment 4 is characterized by comprising the following steps:
the method comprises the following steps: weighing the components in parts by mass;
step two: the components are melted and blended by an internal mixer, the internal mixing temperature is 120 ℃, the internal mixing time is 15 minutes, and then the components are mixed by a reciprocating machine, wherein the reciprocating machine is divided into four areas, and the working temperature of each area is as follows: the temperature of the first zone is 90 ℃, the temperature of the second zone is 170 ℃, the temperature of the third zone is 150 ℃, and the temperature of the fourth zone is 100 ℃;
step three: and (2) granulating the melted and blended materials after sequentially passing through the zones by adopting a single-screw extruder, wherein the single-screw extruder is divided into five zones, and the working temperature of each zone is as follows: the first zone was 100 deg.C, the second zone was 110 deg.C, the third zone was 130 deg.C, the fourth zone was 140 deg.C, and the fifth zone was 150 deg.C.
(example 5)
The insulating material for the photovoltaic cable of embodiment 5 is composed of the following raw materials in parts by mass: 10 parts of ethylene-vinyl acetate copolymer, 10 parts of ethylene butyl acrylate, 10 parts of ethylene propylene diene monomer, 9 parts of metallocene low-density polyethylene, 45 parts of silane coupling agent surface modified aluminum hydroxide, 5 parts of diethyl aluminum phosphinate, 4.5 parts of compatilizer, 3 parts of crosslinking sensitizer, 1 part of antioxidant and 2.5 parts of lubricant.
Wherein the content of vinyl acetate in the ethylene-vinyl acetate copolymer is 22%, and the melt index is (190 ℃, 2.16kg)4g/10 min; the content of butyl acrylate in the ethylene butyl acrylate is 25 percent, and the melt index is (190 ℃, 2.16kg)6g/10 min; the ethylene content of the ethylene-propylene-diene monomer is 59%, the propylene content is 35%, the third monomer is ethylidene-norbornene, the heat resistance of the material is better, the content is 6%, and the Mooney viscosity of the ethylene-propylene-diene monomer is (ML 1+4,125 ℃) 90; the density of the metallocene low density polyethylene is 0.925g/cm3The melt index is (190 ℃, 2.16kg)5g/10 min; the mesh number of the silane coupling agent surface modified aluminum hydroxide is 6000 meshes; the grain diameter D50 of the aluminum diethylphosphinate is less than or equal to 10 mu m, and the decomposition temperature (TGA thermal weight loss is 1%): is > 320 ℃.
The compatilizer is maleic anhydride grafted polyolefin material, the base material is ethylene-vinyl acetate copolymer, and the grafting rate is 2 percent; the crosslinking sensitizer is trimethylolpropane triacrylate, so that the heat resistance, solvent resistance, weather resistance, corrosion resistance and flame retardance of a crosslinking agent product can be obviously improved, and the mechanical property and the electrical property are improved; the antioxidant is 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer; the lubricant is polyethylene wax.
The preparation method of the insulating material for photovoltaic cables of embodiment 5 is characterized by comprising the following steps:
the method comprises the following steps: weighing the components in parts by mass;
step two: the components are melted and blended by an internal mixer, the internal mixing temperature is 140 ℃, the internal mixing time is 5 minutes, and then the components are mixed by a reciprocating machine, wherein the reciprocating machine is divided into four areas, and the working temperature of each area is as follows: the temperature of the first zone is 100 ℃, the temperature of the second zone is 180 ℃, the temperature of the third zone is 160 ℃, and the temperature of the fourth zone is 120 ℃;
step three: and (3) granulating the melted and blended materials after passing through each zone in sequence by adopting a single-screw extruder, wherein the single-screw extruder extrudes the materials at 160 ℃ and the fifth zone is at 160 ℃.
The insulating material for the photovoltaic cables of examples 1 to 5 was extruded to prepare a material having a thickness of 2.5mm2The performance of the insulated core wire is tested after the insulated core wire is irradiated by an electron accelerator according to a proper dose, and the specific data are shown in the following table:
Figure BDA0002614937630000081
Figure BDA0002614937630000091
the invention realizes excellent insulating property, mechanical property and processing property under high filling of the material by reasonably matching the ethylene-vinyl acetate copolymer, the ethylene butyl acrylate, the ethylene propylene diene monomer and the metallocene low-density polyethylene and surface modification of the aluminum hydroxide inorganic flame retardant, the light transmittance in smoke can reach more than 90 percent, and simultaneously the invention can meet the insulating direct current voltage withstand test and low temperature resistance test of 1.8kV at 85 ℃ for 10 days; by compounding an antioxidant system and the high-temperature resistance of ethylene butyl acrylate, the material can pass the service life of more than 25 years at 90 ℃; the flame retardant effect of the material is further improved by adding diethyl aluminum phosphinate as a halogen-free flame retardant.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. The insulating material for the photovoltaic cable is characterized by comprising the following raw materials in parts by mass: 10-30 parts of ethylene-vinyl acetate copolymer, 1-20 parts of ethylene butyl acrylate, 1-10 parts of ethylene propylene diene monomer, 5-20 parts of metallocene low-density polyethylene, 30-60 parts of modified aluminum hydroxide, 1-10 parts of diethyl aluminum phosphinate, 1-5 parts of compatilizer, 0.5-3 parts of crosslinking sensitizer, 0.5-2 parts of antioxidant and 1-5 parts of lubricant.
2. The insulating material for photovoltaic cables as claimed in claim 1, wherein: the content of vinyl acetate in the ethylene-vinyl acetate copolymer is 14-30%.
3. The insulating material for photovoltaic cables as claimed in claim 1, wherein: the content of butyl acrylate in the ethylene butyl acrylate is 20-30%.
4. The insulating material for photovoltaic cables as claimed in claim 1, wherein: the ethylene content of the ethylene-propylene-diene monomer rubber is 50-60%, the propylene content is 35-45%, and the third monomer is ethylidene-norbornene and has a content of 4-6%.
5. The insulating material for photovoltaic cables as claimed in claim 1, wherein: the modified aluminum hydroxide is silane coupling agent surface modified aluminum hydroxide.
6. The insulating material for photovoltaic cables as claimed in claim 1, wherein: the compatilizer is maleic anhydride grafted polyolefin material, the base material is polyethylene, ethylene octene copolymer or ethylene-vinyl acetate copolymer, and the grafting rate is 0.5-2%.
7. The insulating material for photovoltaic cables as claimed in claim 1, wherein: the crosslinking sensitizer is trimethylolpropane triacrylate, triallyl isocyanurate or trimethylolpropane triacrylate.
8. The insulating material for photovoltaic cables as claimed in claim 1, wherein: the antioxidant is one or more of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester, 4' -thiobis (6-tert-butyl-3-methylphenol), 2, 4-trimethyl-1, 2-dihydroquinoline polymer, dilauryl thiodipropionate and distearyl thiodipropionate.
9. The irradiation crosslinking low-smoke halogen-free insulating material for the photovoltaic cable as claimed in claim 1 is characterized in that: the lubricant is one or more of silicone master batch, stearic acid, zinc stearate, calcium stearate and polyethylene wax.
10. A process for the preparation of an insulating material for photovoltaic cables according to any one of claims 1 to 9, characterized in that it comprises the following steps:
the method comprises the following steps: weighing the components in parts by mass;
step two: the components are melted and blended through an internal mixer, the internal mixing temperature is 120-140 ℃, the internal mixing time is 5-15 minutes, and then the components are mixed through a reciprocating machine, wherein the reciprocating machine is divided into four zones, and the working temperature of each zone is as follows: the temperature of the first area is 90-100 ℃, the temperature of the second area is 170-180 ℃, the temperature of the third area is 150-160 ℃, and the temperature of the fourth area is 100-120 ℃;
step three: and (2) granulating the melted and blended materials after sequentially passing through the zones by adopting a single-screw extruder, wherein the single-screw extruder is divided into five zones, and the working temperature of each zone is as follows: the temperature of the first zone is 100-120 ℃, the temperature of the second zone is 110-120 ℃, the temperature of the third zone is 130-140 ℃, the temperature of the fourth zone is 140-160 ℃, and the temperature of the fifth zone is 150-160 ℃.
CN202010766683.7A 2020-08-03 2020-08-03 Insulating material for photovoltaic cable and preparation method thereof Pending CN111961274A (en)

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