CN111732784B - Ultralow-temperature-resistant torsion-resistant halogen-free elastomer cable material for thermoplastic wind energy cable - Google Patents
Ultralow-temperature-resistant torsion-resistant halogen-free elastomer cable material for thermoplastic wind energy cable Download PDFInfo
- Publication number
- CN111732784B CN111732784B CN202010700393.2A CN202010700393A CN111732784B CN 111732784 B CN111732784 B CN 111732784B CN 202010700393 A CN202010700393 A CN 202010700393A CN 111732784 B CN111732784 B CN 111732784B
- Authority
- CN
- China
- Prior art keywords
- resin
- wind energy
- flame retardant
- halogen
- antioxidant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
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
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
-
- 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
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
-
- 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
- C08L23/0861—Saponified vinylacetate
-
- 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
-
- 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
- C08K3/38—Boron-containing compounds
- C08K2003/387—Borates
-
- 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
-
- 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
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
Abstract
The invention relates to a halogen-free elastomer cable material for a thermoplastic wind energy cable, which comprises the following components in percentage by mass: resin A: 25% -30%; resin a comprises a block copolymer of ethylene; resin B: 10% -20%; the resin B comprises one or more of bimodal polyethylene resin, metallocene catalysis reinforced polyethylene resin and linear low-density polyethylene resin; flame retardant: 35% -50%; the flame retardant comprises inorganic clay and expandable graphite; the mass ratio of the inorganic clay to the expandable graphite is 1: 2-5; flame retardant synergist: 2.0% -4.0%; a compatilizer: 5.0% -12.0%; the compatilizer is maleic anhydride graft polymer; surface modification coupling agent: 0.4% -1.2%; the surface modified coupling agent is a siloxane compound; antioxidant: 1.0% -3.0%; lubricant: 1.0% -3.0%; asphaltenes: 1.0% -3.0%; 1.0 to 3.0 percent of low-temperature flexibility modifier; low temperature flexibility modifiers include Elevast polymer modifiers; PBT resin: 0.1 to 0.5 percent.
Description
Technical Field
The invention relates to a wind energy cable material, in particular to an ultralow temperature-resistant torsion-resistant halogen-free elastomer cable material for a thermoplastic wind energy cable.
Background
In the world, petrochemical resources are increasingly in short supply, environmental pollution is increasingly serious, new energy is developed and utilized to become a technology which is more and more important in every country in the world, wind power generation, photovoltaic power generation and the like in some developed countries are gradually increased to be important strategic alternative energy, and the demand of cables for wind power generation (wind energy cables for short) is increased.
At present, most of cable materials of wind energy cables mostly adopt PVC or CPE materials, and the materials belong to halogen-containing materials, so that the health of production personnel is threatened, the environment is polluted, and the requirements of low temperature resistance and torsion resistance are difficult to meet. Most halogen-free flame-retardant wind energy cable materials are vulcanized rubber or cross-linked polyolefin, and the requirements of high temperature resistance, low temperature resistance, high flame retardance, flexibility, oil resistance and solvent resistance are difficult to meet at the same time.
Most wind energy cables need to meet the harsh use conditions of environment temperature resistance of-45 ℃ to 50 ℃, sunlight irradiation, rain and snow invasion, large day and night temperature difference and the like in the operation process; and the cable is continuously twisted in the operation process, so that the cable for wind power generation is required to have the characteristics of excellent torsion resistance, low temperature resistance, weather resistance and the like.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide an ultralow temperature resistant and torsion resistant halogen-free elastomer cable material for a thermoplastic wind energy cable, which is soft, high in elasticity, capable of resisting the environmental temperature of-60 ℃, good in oil resistance and flame retardance, free of crosslinking and free of harmful components such as halogen, heavy metal and the like to the environment, and the cable material for the wind energy cable is high in elasticity and environment temperature resistance.
The halogen-free elastomer cable material for the thermoplastic wind energy cable comprises the following components in percentage by mass:
resin A: 25% -30%; the melt index of the resin A under the condition of 190 ℃ multiplied by 2.16kg is 0.5 to 15.0g/10min (preferably 2.5 to 3.5g/10 min); resin a comprises a block copolymer of ethylene;
resin B: 10% -20%; the molecular weight of the resin B is 10 to 30 ten thousand (preferably 10 to 15 ten thousand); the resin B comprises one or more of bimodal polyethylene resin, metallocene catalysis reinforced polyethylene resin and linear low-density polyethylene resin;
flame retardant: 35% -50%; the flame retardant comprises inorganic clay and expandable graphite; the mass ratio of the inorganic clay to the expandable graphite is 1: 2-5;
flame retardant synergist: 2.0% -4.0%;
a compatilizer: 5.0% -12.0%; the compatilizer is maleic anhydride graft polymer, the grafting rate of the compatilizer is 1.5-2.0%, and the melt index of the compatilizer under the condition of 190 ℃ multiplied by 2.16kg is 0.2-2.0g/10min (preferably 0.2-0.8g/10 min);
surface modification coupling agent: 0.4% -1.2%; the surface modified coupling agent is a siloxane compound;
antioxidant: 1.0% -3.0%;
lubricant: 1.0% -3.0%;
asphaltenes: 1.0% -3.0%;
1.0 to 3.0 percent of low-temperature flexibility modifier; low temperature flexibility modifiers include Elevast polymer modifiers;
PBT resin: 0.1 to 0.5 percent.
Further, the block copolymer of ethylene includes ethylene-vinyl acetate copolymer (EVA), ethylene-methyl methacrylate copolymer (EMA), ethylene-ethyl acrylate copolymer (EEA), ethylene-butyl acrylate copolymer (EBA); ethylene-butene copolymer, ethylene-hexene copolymer, ethylene-octene copolymer, metallocene-catalyzed ethylene-propylene-hexene terpolymer (KN resin), ethylene-propylene-VNB terpolymer (EPDM), ethylene-propylene-ENB-VNB tetrapolymer, and ethylene-vinyl alcohol copolymer (EVOH).
Further, the flame retardant also comprises other flame retardants, the other flame retardants are selected from one or more of aluminum hydroxide, magnesium hydroxide, aluminum hypophosphite, diethyl aluminum hypophosphite, zinc borate, hydrated magnesium aluminum hydrotalcite and barium sulfate, and the mass ratio of the other flame retardants to the inorganic clay is 1-2: 1.
Further, the inorganic clay is selected from one or more of acicular wollastonite, nano montmorillonite, sepiolite and attapulgite; the particle size of the inorganic clay is 1000-2500 meshes.
Further, the flame-retardant synergist is antimony trioxide and polydimethylsiloxane or zinc borate and polydimethylsiloxane.
Further, the maleic anhydride grafted polymer comprises one or more of EPDM-maleic anhydride graft, POE-maleic anhydride graft, PE-maleic anhydride graft and EVA-maleic anhydride graft.
Further, the surface modification coupling agent comprises one or more of vinyl trimethoxy silane, vinyl triethoxy silane, vinyl tri (beta-methoxyethoxy) silane and linear polydimethylsiloxane.
Further, the antioxidant is an antioxidant 1010 (pentaerythrityl tetrakis [ β - (3, 5-di-t-butyl-4-hydroxyphenyl) propionate)), an antioxidant 2246(2,2 '-methylenebis (4-methyl-6-t-butylphenol)), an antioxidant 1035 (thiodiethylenebis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ]), an antioxidant 1024(N, N' -bis [ β - (3, 5-di-t-butyl-4-hydroxyphenyl) propionyl ] hydrazine), or an antioxidant 264(2, 6-di-t-butyl-p-cresol).
Further, the lubricant comprises one or more of glyceryl stearate, oxidized polyethylene wax, EVA wax, calcium stearate and zinc stearate.
Further, the Elevast polymer modifier is an Elevast (TM) polymer modifier from Exxon Mobil.
Further, the glass fiber content of the PBT is 10-30%. The PBT with the glass fiber content can ensure that the cable material has high wear resistance and high enough deformation temperature resistance.
Preferably, the halogen-free elastomer cable material for the thermoplastic wind energy cable comprises the following components in percentage by mass:
resin A: 25% -30%; the resin A is at least two of ethylene-vinyl alcohol copolymer, ethylene-butene copolymer, metallocene-catalyzed ethylene-propylene-hexene terpolymer and ethylene-vinyl alcohol copolymer;
resin B: 10% -20%; the resin B is bimodal polyethylene resin and/or metallocene catalysis reinforced polyethylene resin;
flame retardant: 35% -40%; the flame retardant comprises inorganic clay, expandable graphite and other flame retardants; the other flame retardant is selected from at least two of aluminum hydroxide, magnesium hydroxide, aluminum hypophosphite, diethyl aluminum hypophosphite and hydrated magnesium aluminum hydrotalcite;
flame retardant synergist: 2.0% -3.0%;
a compatilizer: 7.0% -10.0%;
surface modification coupling agent: 0.8% -1.2%; the surface modification coupling agent is one or more of vinyl trimethoxy silane, vinyl triethoxy and vinyl tri (beta-methoxy ethoxy) silane;
antioxidant: 1.0% -2.0%;
lubricant: 1.0% -3.0%;
asphaltenes: 1.0% -3.0%;
1.0 to 3.0 percent of low-temperature flexibility modifier; low temperature flexibility modifiers include Elevast polymer modifiers;
PBT resin: 0.1 to 0.5 percent.
The preparation method of the halogen-free elastomer cable material for the thermoplastic wind energy cable comprises the following steps:
uniformly mixing the flame retardant and the flame retardant synergist at the rotation speed of 200-300rpm, adding the surface modification coupling agent, stirring for 3-10min, sequentially adding the resin A, the resin B, the compatilizer, the antioxidant, the lubricant, the asphaltene, the low-temperature flexible modifier and the PBT resin, stirring for 5-10min again, banburying, extruding, granulating and cooling at the temperature of 130-170 ℃ to obtain the halogen-free elastomer cable material for the thermoplastic wind energy cable.
The halogen-free elastomer cable material for the thermoplastic wind energy cable is not required to be crosslinked after being subsequently prepared into a cable, the preparation process is simple, and the material can be recycled.
By the scheme, the invention at least has the following advantages:
1. in order to improve the flexibility and elasticity of the halogen-free elastomer cable material for the thermoplastic wind energy cable, the resin A with a specific melt index or molecular weight and the resin B with a high molecular weight are compounded, so that the material has better oil resistance on the premise of non-irradiation, can meet the requirement of the oil resistance of a wind energy cable sheath material (902# oil, 100 ℃, 24h, and the retention rate of strength and elongation at break is more than 75 percent), simplifies the production process and reduces the production cost. Wherein, the resin A is a block copolymer of ethylene, and the resin B is polyethylene resin, and the compatibility of the two is better.
2. In order to improve the flame retardance of the halogen-free elastomer cable material for the thermoplastic wind energy cable, the halogen-free elastomer cable material is compounded with a flame retardant and a flame retardant synergist, wherein the flame retardant simultaneously contains inorganic clay and expandable graphite, and the inorganic clay not only has flame retardance, but also can improve the flexibility and elasticity of the cable material. The expandable graphite is a graphite product obtained by taking natural crystalline flake graphite as a raw material and carrying out chemical or electrochemical treatment, and the expandable graphite can be instantly expanded when meeting high temperature and is changed into a worm shape from a sheet shape, so that the structure is loose, porous and bent, the specific surface area is large, the adsorption force is strong, the filling property is good, and the expandable graphite is used in a cable material, so that the dispersity of flame retardant particles and the compatibility with elastomer resin are improved, the improvement of the flame retardant property of the whole material is facilitated, and the smoke density is reduced; the dispersibility of the flame-retardant particles is improved, so that the light transmittance of the final cable material is high.
3. The compatilizer comprises a maleic anhydride grafted polymer with the melt index of 0.2-2.0g/10min, the maleic anhydride grafted polymer is suitable for the elastomer resin composition, and the maleic anhydride grafted polymer with the excessively high or excessively low melt index can not ensure the good compatibility of other components with the elastomer resin composition.
4. By adding a small amount of asphaltene into the halogen-free elastomer cable material for the thermoplastic wind energy cable, the asphaltene is not melted when being heated to more than 300 ℃, only decomposed into gas and coke, and no fraction is available, thereby avoiding the generation of toxic gas after asphalt combustion, having good insulativity and waterproofness, improving the service condition of the cable and prolonging the service life.
5. The low-temperature flexibility modifier is added into the cable material, so that the low-temperature flexibility modifier has a synergistic enhancement effect with the block copolymer of ethylene and the polyethylene resin in the cable material, and the low-temperature flexibility modifier has excellent low-temperature resistance performance of the material, reduces the glass transition temperature of the resin and improves the flexibility performance of the material at a lower temperature.
6. Because the addition amount of the PBT resin is less, the insulation property of the cable material is not influenced. The PBT resin with a small amount is added into the cable material, so that on one hand, the PBT resin has good affinity with a flame retardant and can play a certain flame retardant effect, and meanwhile, due to the crystallinity, a tiny crystal unit is formed in the cable material, so that the low-temperature flexibility of the cable material is improved.
7. Through the synergistic effect of the components, the halogen-free elastomer cable material for the thermoplastic wind energy cable has low hardness (78A), softness, high elasticity and torsion resistance, and particularly passes a torsion test (2500 times (2000 standard requirements)) at ultralow temperature (-60 ℃ (55 standard temperature)). The cable material disclosed by the invention has high flame retardant property after being prepared into a wire, can pass IEC60332-3-24C flame retardant test, and has low smoke density and light transmittance up to 86% (60% of standard requirement).
The foregoing is a summary of the present invention, and in order to provide a clear understanding of the technical means of the present invention and to be implemented in accordance with the present specification, the following is a preferred embodiment of the present invention and is described in detail below.
Detailed Description
The following examples are given to further illustrate the embodiments of the present invention. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
In the following examples of the present invention, unless otherwise specified, all of the low-temperature flexibility modifiers are Elevast (TM) polymer modifiers from Exxon Mobil. The melt index of the resin A under the condition of 190 ℃ multiplied by 2.16kg is 2.5-3.5g/10 min. The molecular weight of the resin B is 10-15 ten thousand. The melt index of the compatilizer under the condition of 190 ℃ multiplied by 2.16kg is 0.2-0.8g/10 min.
Example 1
The invention relates to a halogen-free elastomer cable material for a thermoplastic wind energy cable, which comprises the following components in percentage by mass:
the flame-retardant modified PBT resin comprises a resin A30%, a resin B20%, a flame retardant 35%, a flame-retardant synergist 2%, a compatilizer 7%, a surface modification coupling agent 0.8%, an antioxidant 1.1%, a lubricant 1%, an asphaltene 1%, a low-temperature flexible modifier 2% and a PBT resin 0.1%.
Wherein, the resin A consists of EVM and ethylene-butylene copolymer with equal mass.
Resin B is a bimodal polyethylene resin.
The flame retardant is inorganic clay, expandable graphite, hydrated magnesium aluminum hydrotalcite and aluminum hypophosphite, and the mass ratio of the inorganic clay to the expandable graphite to the hydrated magnesium aluminum hydrotalcite to the aluminum hypophosphite is 1:2: 1. The inorganic clay is needle-shaped wollastonite, and the particle size of the inorganic clay is 1000-2500 meshes.
The flame-retardant synergist consists of antimony trioxide and polydimethylsiloxane with equal mass.
The compatilizer is POE-maleic anhydride graft and PE-maleic anhydride graft, and the mass ratio of the POE-maleic anhydride graft to the PE-maleic anhydride graft is 2: 1.
The surface modified coupling agent is vinyl trimethoxy silane.
The antioxidant is antioxidant 1010.
The lubricant is equal-mass glyceryl stearate and oxidized polyethylene wax.
The glass fiber content of the PBT resin is 10 percent.
Example 2
The invention relates to a halogen-free elastomer cable material for a thermoplastic wind energy cable, which comprises the following components in percentage by mass:
the flame-retardant modified PBT resin comprises, by weight, resin A30%, resin B20%, a flame retardant 35%, a flame-retardant synergist 2%, a compatilizer 7%, a surface modification coupling agent 0.8%, an antioxidant 1.1%, a lubricant 1%, asphaltene 1%, a low-temperature flexibility modifier 2% and a PBT resin 0.1%.
Wherein, the resin A consists of EVM, ethylene-butylene copolymer and ethylene-vinyl alcohol copolymer with equal mass.
The resin B is bimodal polyethylene resin with equal mass and metallocene catalysis reinforced polyethylene resin.
The flame retardant is inorganic clay, expandable graphite, hydrated magnesium aluminum hydrotalcite and diethyl aluminum hypophosphite, and the mass ratio of the inorganic clay to the expandable graphite to the hydrated magnesium aluminum hydrotalcite to the aluminum hypophosphite is 1:2: 1. The inorganic clay is nano montmorillonite with the particle size of 1000-2000 meshes.
The flame-retardant synergist consists of zinc borate and polydimethylsiloxane with equal mass.
The compatilizer is an EVA-maleic anhydride graft and a PE-maleic anhydride graft, and the mass ratio of the EVA-maleic anhydride graft to the PE-maleic anhydride graft is 2: 1.
The surface modifying coupling agent is vinyl trimethoxy silane and vinyl tri (beta-methoxy ethoxy) silane with equal mass.
The antioxidant is antioxidant 1035.
The lubricant is equal-quality EVA wax and oxidized polyethylene wax.
The glass fiber content of the PBT resin is 10 percent.
Example 3
The invention relates to a halogen-free elastomer cable material for a thermoplastic wind energy cable, which comprises the following components in percentage by mass:
25% of resin A, 20% of resin B, 38% of flame retardant, 2.5% of flame retardant synergist, 8% of compatilizer, 1% of surface modification coupling agent, 2% of antioxidant, 1% of lubricant, 1.2% of asphaltene, 1% of low-temperature flexible modifier and 0.3% of PBT resin.
The specific materials of the components used in this example were the same as in example 1.
Example 4
The invention relates to a halogen-free elastomer cable material for a thermoplastic wind energy cable, which comprises the following components in percentage by mass:
25% of resin A, 20% of resin B, 38% of flame retardant, 2.5% of flame retardant synergist, 8% of compatilizer, 1% of surface modification coupling agent, 2% of antioxidant, 1% of lubricant, 1.2% of asphaltene, 1% of low-temperature flexible modifier and 0.3% of PBT resin.
The specific materials of the components used in this example were the same as in example 2.
Example 5
The invention relates to a halogen-free elastomer cable material for a thermoplastic wind energy cable, which comprises the following components in percentage by mass:
26% of resin A, 10% of resin B, 40% of flame retardant, 3% of flame retardant synergist, 10% of compatilizer, 1.2% of surface modification coupling agent, 1% of antioxidant, 3% of lubricant, 2.5% of asphaltene, 2.8% of low-temperature flexible modifier and 0.5% of PBT resin.
The specific materials of the components used in this example were the same as in example 1.
Example 6
The invention relates to a halogen-free elastomer cable material for a thermoplastic wind energy cable, which comprises the following components in percentage by mass:
26% of resin A, 10% of resin B, 40% of flame retardant, 3% of flame retardant synergist, 10% of compatilizer, 1.2% of surface modification coupling agent, 1% of antioxidant, 3% of lubricant, 2.5% of asphaltene, 2.8% of low-temperature flexible modifier and 0.5% of PBT resin.
The specific materials of the components used in this example were the same as in example 2.
Example 7
The invention relates to a halogen-free elastomer cable material for a thermoplastic wind energy cable, which comprises the following components in percentage by mass:
25% of resin A, 15% of resin B, 48% of flame retardant, 2% of flame retardant synergist, 5% of compatilizer, 0.5% of surface modification coupling agent, 1% of antioxidant, 1% of lubricant, 1.2% of asphaltene, 1.2% of low-temperature flexible modifier and 0.1% of PBT resin.
The specific materials of the components used in this example were the same as in example 1.
Example 8
The invention relates to a halogen-free elastomer cable material for a thermoplastic wind energy cable, which comprises the following components in percentage by mass:
25% of resin A, 12% of resin B, 35% of flame retardant, 4% of flame retardant synergist, 11.4% of compatilizer, 0.6% of surface modification coupling agent, 3% of antioxidant, 2.5% of lubricant, 3% of asphaltene, 3% of low-temperature flexible modifier and 0.5% of PBT resin.
The specific materials of the components used in this example were the same as in example 2.
In the above embodiments, the preparation method of the halogen-free elastomer cable material for the thermoplastic wind energy cable in each embodiment is as follows:
adding a flame retardant and a flame retardant synergist into a high-speed mixer, starting stirring at the rotation speed of 200-.
Comparative example 1
The halogen-free elastomer cable material for the thermoplastic wind energy cable as the comparative example comprises the following components in percentage by mass:
30% of resin A, 23% of resin B, 35% of flame retardant, 2% of flame retardant synergist, 7% of compatilizer, 0.9% of surface modification coupling agent, 1.1% of antioxidant and 1% of lubricant.
The specific materials of the components used in this example were the same as in example 1.
Comparative example 2
The halogen-free elastomer cable material for the thermoplastic wind energy cable as the comparative example comprises the following components in percentage by mass:
30% of resin A, 20% of resin B, 35% of flame retardant, 2% of flame retardant synergist, 7% of compatilizer, 0.5% of surface modification coupling agent, 1.5% of antioxidant, 1% of lubricant and 1% of asphaltene.
The specific materials of the components used in this example were the same as in example 1.
Comparative example 3
The halogen-free elastomer cable material for the thermoplastic wind energy cable as the comparative example comprises the following components in percentage by mass:
30% of resin A, 20% of resin B, 35% of flame retardant, 2% of flame retardant synergist, 7% of compatilizer, 0.5% of surface modification coupling agent, 1.5% of antioxidant, 2% of lubricant, 2% of asphaltene and 2% of low-temperature flexible modifier.
The specific materials of the components used in this example were the same as in example 1.
Comparative example 4
The halogen-free elastomer cable material for the thermoplastic wind energy cable as the comparative example comprises the following components in percentage by mass:
45% of resin A, 38% of flame retardant, 2.5% of flame retardant synergist, 8% of compatilizer, 1% of surface modification coupling agent, 2% of antioxidant, 1% of lubricant, 1.2% of asphaltene, 1% of low-temperature flexible modifier and 0.3% of PBT resin.
The specific materials of the components used in this example were the same as in example 1.
In addition, in order to investigate the effect of different parameters of resin a and resin B on the performance of the halogen-free elastomer cable material for thermoplastic wind energy cables, comparative examples 5 to 8 were also provided below:
the formulation composition of comparative example 5 is the same as example 1 except that the melt index of the EVM and the ethylene-butene copolymer at 190 ℃ C. times.2.16 kg is 1.0g/10 min.
The formulation composition of comparative example 6 is the same as example 1 except that the melt index of the EVM and the ethylene-butene copolymer at 190 ℃ C. times.2.16 kg is 30.0g/10 min.
The formulation composition of comparative example 7 was the same as example 1 except that the molecular weight of the bimodal polyethylene resin was 2-5 ten thousand.
The formulation composition of comparative example 8 was the same as example 1 except that the molecular weight of the bimodal polyethylene resin was 40-50 ten thousand.
The performance test data of the halogen-free elastomer cable material for the thermoplastic wind energy cable prepared in the examples and the comparative examples are shown in tables 1-2:
TABLE 1 Properties of halogen-free elastomer cable materials for different thermoplastic wind energy cables according to the present invention
Table 2 comparative examples properties of halogen-free elastomer cable materials for different thermoplastic wind energy cables
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, it should be noted that, for those skilled in the art, many modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (5)
1. The halogen-free elastomer cable material for the thermoplastic wind energy cable is characterized by comprising the following components in percentage by mass:
resin A: 25% -30%; the melt index of the resin A under the condition of 190 ℃ multiplied by 2.16kg is 2.5-3.5g/10 min; the resin A is at least two of ethylene-vinyl alcohol copolymer, ethylene-butylene copolymer and ethylene-vinyl alcohol copolymer;
resin B: 10% -20%; the molecular weight of the resin B is 10-15 ten thousand; the resin B comprises a bimodal polyethylene resin and/or a metallocene catalysis reinforced polyethylene resin;
flame retardant: 35% -40%; the flame retardant comprises inorganic clay, expandable graphite and other flame retardants; the other flame retardant is selected from at least two of aluminum hydroxide, magnesium hydroxide, aluminum hypophosphite, diethyl aluminum hypophosphite and hydrated magnesium aluminum hydrotalcite; the inorganic clay is selected from one or more of acicular wollastonite, nano montmorillonite, sepiolite and convex-concave attapulgite;
flame retardant synergist: 2.0% -3.0%; the flame-retardant synergist is antimony trioxide and polydimethylsiloxane or zinc borate and polydimethylsiloxane;
a compatilizer: 7.0% -10.0%; the compatilizer is one or more of EPDM-maleic anhydride graft, POE-maleic anhydride graft, PE-maleic anhydride graft and EVA-maleic anhydride graft; the grafting rate of the compatilizer is 1.5-2.0%, and the melt index of the compatilizer under the condition of 190 ℃ multiplied by 2.16kg is 0.2-2.0g/10 min;
surface modification coupling agent: 0.8% -1.2%; the surface modification coupling agent is one or more of vinyl trimethoxy silane, vinyl triethoxy and vinyl tri (beta-methoxy ethoxy) silane;
antioxidant: 1.0% -2.0%;
lubricant: 1.0% -3.0%;
asphaltenes: 1.0% -3.0%;
1.0 to 3.0 percent of low-temperature flexibility modifier; the low temperature flexibility modifier comprises an Elevast polymer modifier;
PBT resin: 0.1% -0.5%; the glass fiber content of the PBT resin is 10-30%.
2. The halogen-free elastomer cable material for thermoplastic wind energy cables as claimed in claim 1, wherein: the mass ratio of the other flame retardants to the inorganic clay is 1-2: 1.
3. The halogen-free elastomer cable material for thermoplastic wind energy cables as claimed in claim 1, wherein: the particle size of the inorganic clay is 1000-2500 meshes.
4. The halogen-free elastomer cable material for thermoplastic wind energy cables as claimed in claim 1, wherein: the antioxidant is antioxidant 1010, antioxidant 2246, antioxidant 1035, antioxidant 1024 or antioxidant 264.
5. The halogen-free elastomer cable material for thermoplastic wind energy cables as claimed in claim 1, wherein: the lubricant comprises one or more of glyceryl stearate, oxidized polyethylene wax, EVA wax, calcium stearate and zinc stearate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010700393.2A CN111732784B (en) | 2020-07-20 | 2020-07-20 | Ultralow-temperature-resistant torsion-resistant halogen-free elastomer cable material for thermoplastic wind energy cable |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010700393.2A CN111732784B (en) | 2020-07-20 | 2020-07-20 | Ultralow-temperature-resistant torsion-resistant halogen-free elastomer cable material for thermoplastic wind energy cable |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111732784A CN111732784A (en) | 2020-10-02 |
| CN111732784B true CN111732784B (en) | 2022-03-11 |
Family
ID=72655190
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010700393.2A Active CN111732784B (en) | 2020-07-20 | 2020-07-20 | Ultralow-temperature-resistant torsion-resistant halogen-free elastomer cable material for thermoplastic wind energy cable |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111732784B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112480536B (en) * | 2020-11-27 | 2023-04-14 | 江苏金发科技新材料有限公司 | Polypropylene composition and preparation and application thereof |
| CN112961424A (en) * | 2021-01-16 | 2021-06-15 | 江西江缆科技有限公司 | Halogen-free flame-retardant fireproof cable and preparation method thereof |
| CN113380447B (en) * | 2021-07-08 | 2022-02-15 | 苏州美昱高分子材料有限公司 | Cable for energy storage system |
| CN113593760B (en) * | 2021-08-04 | 2022-05-03 | 苏州美昱高分子材料有限公司 | Low-smoke halogen-free flame-retardant battery connecting cable for power energy storage system |
| CN115353817B (en) * | 2022-10-20 | 2022-12-23 | 衡水中裕铁信防水技术有限公司 | Prefabricated low-temperature-resistant rubber asphalt waterproof coiled material and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2734581A1 (en) * | 2008-08-21 | 2010-02-25 | Lanxess Deutschland Gmbh | Highly flexible, halogen-free and flame-retardant thermoplastic cable mixtures |
| CN105778248A (en) * | 2014-12-25 | 2016-07-20 | 上海凯波特种电缆料厂有限公司 | 150-DEG radiation-crosslinked flame-retardant polyolefin material for electric car high-voltage cable, and preparation method thereof |
| CN107629359A (en) * | 2017-10-13 | 2018-01-26 | 四会市启德信息咨询服务有限公司 | A kind of abrasion resistant fire blocking cable jacket material |
| CN110903538A (en) * | 2019-12-05 | 2020-03-24 | 中广核三角洲（苏州）高聚物有限公司 | 90-DEG C cracking-resistant moisture-proof flame-retardant polyethylene cable material and preparation method thereof |
-
2020
- 2020-07-20 CN CN202010700393.2A patent/CN111732784B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2734581A1 (en) * | 2008-08-21 | 2010-02-25 | Lanxess Deutschland Gmbh | Highly flexible, halogen-free and flame-retardant thermoplastic cable mixtures |
| CN105778248A (en) * | 2014-12-25 | 2016-07-20 | 上海凯波特种电缆料厂有限公司 | 150-DEG radiation-crosslinked flame-retardant polyolefin material for electric car high-voltage cable, and preparation method thereof |
| CN107629359A (en) * | 2017-10-13 | 2018-01-26 | 四会市启德信息咨询服务有限公司 | A kind of abrasion resistant fire blocking cable jacket material |
| CN110903538A (en) * | 2019-12-05 | 2020-03-24 | 中广核三角洲（苏州）高聚物有限公司 | 90-DEG C cracking-resistant moisture-proof flame-retardant polyethylene cable material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111732784A (en) | 2020-10-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111732784B (en) | Ultralow-temperature-resistant torsion-resistant halogen-free elastomer cable material for thermoplastic wind energy cable | |
| CN111533987B (en) | Halogen-free cross-linked polyolefin cable material for energy storage cable | |
| CN101679717B (en) | Process for producing flame retardant silane-crosslinked olefin resin, electric insulated wire, and process for manufacturing electric insulated wire | |
| CN111647265B (en) | Oil-resistant low-smoke halogen-free flame-retardant flexible polyurethane cable material and preparation method thereof | |
| WO2015043121A1 (en) | Zero-halogen cable insulation material for 125°c irradiation cross-linked epcv photovoltaics, and method for preparation thereof | |
| WO2010020586A1 (en) | Highly flexible, halogen-free and fire-resistant thermoplastic cable mixtures | |
| EP0869992B1 (en) | Process for producing flame-retardant, silane-crosslinked polyolefin | |
| CN104829936A (en) | High-elongation flame-retardant cable material manufacturing process | |
| CN106589750B (en) | A kind of Halogen-free flame retardant sheath material of low-heat rate of release | |
| CN105504467A (en) | Preparation process of high-tensile-strength insulating rubber cable material | |
| WO2018180689A1 (en) | Flame-retardant crosslinked resin molded article, production method therefor, silane masterbatch, masterbatch mixture, molded article thereof, and flame-retardant product | |
| CN103073756A (en) | High-ductility, low-smoke, environment-friendly, flame-retardant and oil-proof cable material | |
| CN111961274A (en) | Insulating material for photovoltaic cable and preparation method thereof | |
| CN102731919A (en) | High-speed-extruding oil-proof wear-resisting irradiation crosslinking rubber material and preparation method thereof | |
| CN114133657A (en) | Preparation method of high-performance flame-retardant low-smoke halogen-free polyolefin cable material | |
| CN114213741A (en) | Hot-water-resistant oil-resistant thermoplastic low-smoke halogen-free flame-retardant polyolefin cable material | |
| CN112521675B (en) | Insulating cold-resistant cable material and preparation method and application thereof | |
| JP5128175B2 (en) | Resin composition and molded body | |
| CN113980301A (en) | Ultraviolet irradiation crosslinking high-electrical-property charging pile insulated cable material for electric automobile and preparation method thereof | |
| CN111909444A (en) | Cross-linking oil-resistant low-temperature-resistant low-smoke halogen-free flame-retardant cable material | |
| CN111875869A (en) | Low-smoke halogen-free flame-retardant polyolefin cable material based on silane copolymer, preparation method thereof and cable | |
| JP4159685B2 (en) | Flame retardant crosslinked resin composition | |
| CN107118496A (en) | A kind of thermoplasticity new-energy automobile power cable material and preparation method thereof | |
| CN115028919B (en) | High-flexibility high-flame-retardance elastomer cable material resistant to high temperature of 150 ℃, preparation method and application thereof | |
| CN115449152B (en) | Flame-retardant antistatic polypropylene composition, flame-retardant antistatic polypropylene material, preparation method and application thereof, mining pipe and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |