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CN114989554B - Low-dielectric-loss halogen-free flame-retardant cable material and preparation method thereof - Google Patents

Low-dielectric-loss halogen-free flame-retardant cable material and preparation method thereof Download PDF

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CN114989554B
CN114989554B CN202210682905.6A CN202210682905A CN114989554B CN 114989554 B CN114989554 B CN 114989554B CN 202210682905 A CN202210682905 A CN 202210682905A CN 114989554 B CN114989554 B CN 114989554B
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halogen
area
free flame
temperature
flame retardant
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CN114989554A (en
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徐鑫森
刘家诚
张�成
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Opta Polymer Jiangsu Co ltd
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Opta Polymer Jiangsu 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
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
    • 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
    • B29C48/285—Feeding the extrusion material to the extruder
    • B29C48/287—Raw material pre-treatment while feeding
    • 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
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/365—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using pumps, e.g. piston pumps
    • 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
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • 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
    • 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
    • C08L23/16—Ethene-propene or ethene-propene-diene copolymers
    • 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
    • H01B3/42—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 polyesters; polyethers; polyacetals
    • H01B3/421—Polyesters
    • 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
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/2224—Magnesium hydroxide
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    • 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
    • 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

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Abstract

The application discloses a low-dielectric-loss halogen-free flame-retardant cable material and a preparation method thereof, wherein the low-dielectric-loss halogen-free flame-retardant cable material comprises the following components: polyethylene, styrene-ethylene-butylene-styrene block copolymer, ethylene propylene rubber, halogen-free flame retardant, red phosphorus, tridecyl alcohol polyoxyethylene ether phosphate, antioxidant auxiliary agent, ethyl acetate, and 2, 5-dimethyl-2, 5-bishexane; the low-dielectric-loss halogen-free flame-retardant cable material product prepared by the application has the characteristics of smooth appearance, excellent flame retardance, low polarization loss and low free loss. The flame-retardant cable has the remarkable advantages of good flame retardant property, reduced signal attenuation, long transmission distance and the like when transmitting high-frequency signals.

Description

Low-dielectric-loss halogen-free flame-retardant cable material and preparation method thereof
Technical Field
The application belongs to the technical field of cable materials, and particularly relates to a low-dielectric-loss halogen-free flame-retardant cable material and a preparation method thereof.
Background
In the prior art, cables for long distance high frequency signal transmission typically use non-flame retardant polyethylene as the insulation and jacket material. Because the polyethylene has the advantages of small dielectric loss angle, good insulating property and stable physical and chemical properties. However, the polyethylene has poor flame retardant property, and when a fire disaster occurs, the polyethylene can form a melt flow, so that the combustion range is enlarged, and the hazard of the fire disaster is increased. However, the polyethylene subjected to flame retardant modification in the market has better flame retardant property, but because the strong polar resin, the flame retardant and the compatilizer with large proportion are added, the cable made of the material generates higher polarization loss when transmitting signals; meanwhile, as the decomposition temperature of the traditional flame retardant is lower, trace bubbles are easy to generate during the production of the cable material, and further, free loss can be generated in the wire and cable made of the cable material. Under the influence of the two factors, the traditional commercial low-smoke halogen-free flame-retardant cable material cannot be used for manufacturing cables for long-distance high-frequency signal transmission.
Disclosure of Invention
This section is intended to outline some aspects of embodiments of the application and to briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section as well as in the description of the application and in the title of the application, which may not be used to limit the scope of the application.
The present application has been made in view of the above and/or problems occurring in the prior art.
Therefore, the application aims to overcome the defects in the prior art and provide the halogen-free flame-retardant cable material with low dielectric loss.
In order to solve the technical problems, the application provides the following technical scheme: comprising the steps of (a) a step of,
polyethylene, styrene-ethylene-butylene-styrene block copolymer, ethylene propylene rubber, halogen-free flame retardant, red phosphorus, surface treating agent, antioxidant auxiliary agent, diluent and 2, 5-dimethyl-2, 5-bishexane.
As a preferred embodiment of the present application, wherein: the halogen-free flame-retardant cable material comprises the following components in percentage by mass: 8-15% of polyethylene, 10-15% of styrene-ethylene-butylene-styrene segmented copolymer, 10-15% of ethylene propylene rubber, 45-60% of halogen-free flame retardant, 1-4% of red phosphorus, 1-2% of surface treatment agent, 1-3% of antioxidant auxiliary agent, 1-2% of diluent and 0.01-0.05% of 2, 5-dimethyl-2, 5-bishexane, wherein the sum of the mass percentages of the components is 100%.
As a preferred embodiment of the present application, wherein: the density of the styrene-ethylene-butylene-styrene block copolymer is 0.910g/cm 3 Styrene content 33%; the density of the ethylene propylene rubber is 0.87g/cm 3 Wherein the mass percentage of ethylene is 70%.
As a preferred embodiment of the present application, wherein: the halogen-free flame retardant is magnesium hydroxide, and the purity is more than or equal to 99.5 percent.
As a preferred embodiment of the present application, wherein: the antioxidant auxiliary agent is prepared by mixing disulfide and tetra-4, 4-diphenyl diphosphite together according to the mass ratio of 1:1.
As a preferred embodiment of the present application, wherein: the diluent is ethyl acetate, and the purity is more than or equal to 98%.
It is still another object of the present application to overcome the deficiencies of the prior art and to provide a method for preparing a low dielectric loss halogen free flame retardant cable material.
In order to solve the technical problems, the application provides the following technical scheme: comprising the steps of (a) a step of,
weighing the following components in percentage by mass:
adding the halogen-free flame retardant into a high-speed mixer, adding the mixed surface treatment agent and diluent into the high-speed mixer through a nozzle, and mixing until the diluent is completely discharged, thus obtaining the treated halogen-free flame retardant;
adding the treated halogen-free flame retardant, polyethylene, styrene-ethylene-butylene-styrene block copolymer, ethylene propylene rubber, red phosphorus and an antioxidant auxiliary agent into a pressurized internal mixer, and mixing to obtain a soft jelly;
and (3) putting the obtained jelly into a double-screw extruder, feeding 2, 5-dimethyl-2, 5-double hexane into a machine barrel in the process, extruding to obtain a granular cable material, air-cooling and packaging.
As a preferred embodiment of the present application, wherein: the double-screw extruder is connected with a vacuum pump, wherein the temperature of a first area is 130-145 ℃, the temperature of a second area is 130-145 ℃, the temperature of a third area is 130-145 ℃, the temperature of a fourth area is 130-145 ℃, the temperature of a fifth area is 130-145 ℃, the temperature of a sixth area is 130-145 ℃, the temperature of a seventh area is 130-145 ℃, the temperature of an eighth area is 130-145 ℃, the temperature of a ninth area is 130-145 ℃, the temperature of a die head is 140-155 ℃, and the pressure of the vacuum pump is set to be 0.1-0.2 ATM.
As a preferred embodiment of the present application, wherein: the 2, 5-dimethyl-2, 5-bishexane is fed into the barrel, wherein the feeding is by lateral feeding in the third zone.
The application has the beneficial effects that:
(1) The application selects the surface treating agent with very low polarity of tridecyl alcohol polyoxyethylene ether phosphate to modify the halogen-free flame retardant, which can not only enhance the compatibility of the flame retardant and the base material resin, but also reduce the polarity of the halogen-free flame retardant.
(2) According to the application, the low-boiling-point nontoxic ethyl acetate is selected as the diluent, so that the tridecyl alcohol polyoxyethylene ether phosphate serving as the surface treatment agent can be coated on the surface of the flame retardant more uniformly, and meanwhile, after being mixed for a certain time in a high-temperature high-speed mixer, the tridecyl alcohol polyoxyethylene ether phosphate can be completely removed, and the material performance is not affected.
(3) The application utilizes the characteristic of good filling property of two resins of ethylene-butylene-styrene block copolymer and ethylene propylene rubber and simultaneously adopts a nonpolar material, so that the two materials are selected to replace ethylene-vinyl acetate copolymer with very high polarity which can be used in the traditional low-smoke halogen-free flame retardant material, and the polarity of the material can be effectively reduced while the mechanical property is stable.
(4) In the application, when the material is extruded by a double screw, the bi-di-penta (2, 5-dimethyl-2, 5-bishexane) is injected into a machine barrel by a micro metering pump from a third section. Because the reaction activity of the Bispenta at high temperature is very high, if the Bispenta reacts with resin in an internal mixing kettle directly, air can be in direct contact with high-temperature rubber compound, oxygen in the air can react with free radicals generated by Bispenta decomposition, so that the Bispenta utilization rate is incomplete, and further fluctuation of physical and chemical properties of materials is caused.
(5) The application is connected with the vacuum pump on the double screw to manufacture a negative pressure environment, so that trace water vapor, air, low molecular compounds and the like contained in the material can be further removed, the material particles are more compact, and the free loss of the cable is reduced.
Detailed Description
In order that the above-recited objects, features and advantages of the present application will become more apparent, a more particular description of the application will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present application, but the present application may be practiced in other ways other than those described herein, and persons skilled in the art will readily appreciate that the present application is not limited to the specific embodiments disclosed below.
Further, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic can be included in at least one implementation of the application. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
The raw materials used in the application are all commonly and commercially available, wherein:
polyethylene density of 0.912g/cm 3 Melt index 2.0g/10min (190 ℃ C. 2.16 kg), dielectric loss factor less than or equal to 0.002, extrusion grade;
the ethylene-butylene-styrene block copolymer (SEBS) has a linear structure and a density of 0.910g/cm 3 Styrene content 33%, 10% toluene solution viscosity 1500mpa.s at 25 ℃;
ethylene propylene rubber density of 0.87g/cm 3 Wherein the mass percentage of ethylene is 70%, the Mooney viscosity of the ethylene propylene rubber is 70MU, and the content of a third monomer ENB is 5%;
magnesium hydroxide, particle size D50: 80-100 nm, D90 less than or equal to 300nm, purity more than or equal to 99.5%;
red phosphorus with the grain diameter D50 less than or equal to 5 mu m and the D90 less than or equal to 10 mu m and the purity more than 95 percent;
tridecyl alcohol polyoxyethylene ether phosphate, industrial grade, purity more than or equal to 95%, and light yellow liquid appearance;
ethyl acetate is industrial grade, the purity is more than or equal to 98 percent, and the appearance is transparent liquid;
2, 5-dimethyl-2, 5-bishexane (hereinafter referred to as bisbipenta) is of industrial grade and has a purity of 99%.
Example 1
Weighing the following components in percentage by mass:
10% of polyethylene, 13% of styrene-ethylene-butylene-styrene block copolymer, 12% of ethylene propylene rubber, 57% of magnesium hydroxide, 4% of red phosphorus, 1.2% of tridecyl alcohol polyoxyethylene ether phosphate, 1.58% of antioxidant auxiliary agent, 1.2% of ethyl acetate and 0.02% of 2, 5-dimethyl-2, 5-bishexane.
Adding magnesium hydroxide into a high-speed mixer, setting the rotating speed of the high-speed mixer to 2000rpm and setting the temperature to 145 ℃; uniformly mixing tridecyl alcohol polyoxyethylene ether phosphate and ethyl acetate, adding the mixture into a high-speed mixer at a speed of 200ml/min through a nozzle, simultaneously increasing the rotating speed of the high-speed mixer to 3000rpm, mixing for 8min, and completely removing the ethyl acetate serving as a diluent to obtain the treated halogen-free flame retardant;
adding the treated halogen-free flame retardant, polyethylene, styrene-ethylene-butylene-styrene segmented copolymer, ethylene propylene rubber, red phosphorus and an antioxidant auxiliary agent into a pressurized internal mixer, controlling the maximum pressure of the internal mixer to be 3MPa, and mixing the components to 175 ℃ in the internal mixer to uniformly mix the components to obtain a mixed soft jelly;
the obtained mixed soft jelly is put into a double-screw extruder connected with a vacuum pump for extrusion, and 2, 5-dimethyl-2, 5-double-hexane is fed into a machine barrel through lateral feeding in a third zone, wherein the temperature of the double-screw extruder is as follows: 130-145 ℃ in the first area, 130-145 ℃ in the second area, 130-145 ℃ in the third area, 130-145 ℃ in the fourth area, 130-145 ℃ in the fifth area, 130-145 ℃ in the sixth area, 130-145 ℃ in the seventh area, 130-145 ℃ in the eighth area, 130-145 ℃ in the ninth area, 130-145 ℃ in the die head, 140-155 ℃ and the vacuum pump pressure is set to be 0.1-0.2 ATM;
through the process, the cable material extruded into particles can be obtained and packaged after air cooling.
Example 2
Weighing the following components in percentage by mass:
9% of polyethylene, 12% of styrene-ethylene-butylene-styrene block copolymer, 14% of ethylene propylene rubber, 58% of magnesium hydroxide, 3% of red phosphorus, 1.3% of tridecyl alcohol polyoxyethylene ether phosphate, 1.37% of antioxidant auxiliary agent, 1.3% of ethyl acetate and 0.03% of 2, 5-dimethyl-2, 5-bishexane.
Adding magnesium hydroxide into a high-speed mixer, setting the rotating speed of the high-speed mixer to 2000rpm and setting the temperature to 145 ℃; uniformly mixing tridecyl alcohol polyoxyethylene ether phosphate and ethyl acetate, adding the mixture into a high-speed mixer at a speed of 200ml/min through a nozzle, simultaneously increasing the rotating speed of the high-speed mixer to 3000rpm, mixing for 8min, and completely removing the ethyl acetate serving as a diluent to obtain the treated halogen-free flame retardant;
adding the treated halogen-free flame retardant, polyethylene, styrene-ethylene-butylene-styrene segmented copolymer, ethylene propylene rubber, red phosphorus and an antioxidant auxiliary agent into a pressurized internal mixer, controlling the maximum pressure of the internal mixer to be 3MPa, and mixing the components to 175 ℃ in the internal mixer to uniformly mix the components to obtain a mixed soft jelly;
the obtained mixed soft jelly is put into a double-screw extruder connected with a vacuum pump for extrusion, and 2, 5-dimethyl-2, 5-double-hexane is fed into a machine barrel through lateral feeding in a third zone, wherein the temperature of the double-screw extruder is as follows: 130-145 ℃ in the first area, 130-145 ℃ in the second area, 130-145 ℃ in the third area, 130-145 ℃ in the fourth area, 130-145 ℃ in the fifth area, 130-145 ℃ in the sixth area, 130-145 ℃ in the seventh area, 130-145 ℃ in the eighth area, 130-145 ℃ in the ninth area, 130-145 ℃ in the die head, 140-155 ℃ and the vacuum pump pressure is set to be 0.1-0.2 ATM;
through the process, the cable material extruded into particles can be obtained and packaged after air cooling.
Example 3
Weighing the following components in percentage by mass:
12% of polyethylene, 11% of styrene-ethylene-butylene-styrene block copolymer, 11% of ethylene propylene rubber, 59% of magnesium hydroxide, 2% of red phosphorus, 1.5% of tridecyl alcohol polyoxyethylene ether phosphate, 1.97% of antioxidant auxiliary agent, 1.5% of ethyl acetate and 0.03% of 2, 5-dimethyl-2, 5-bishexane.
Adding magnesium hydroxide into a high-speed mixer, setting the rotating speed of the high-speed mixer to 2000rpm and setting the temperature to 145 ℃; uniformly mixing tridecyl alcohol polyoxyethylene ether phosphate and ethyl acetate, adding the mixture into a high-speed mixer at a speed of 200ml/min through a nozzle, simultaneously increasing the rotating speed of the high-speed mixer to 3000rpm, mixing for 8min, and completely removing the ethyl acetate serving as a diluent to obtain the treated halogen-free flame retardant;
adding the treated halogen-free flame retardant, polyethylene, styrene-ethylene-butylene-styrene segmented copolymer, ethylene propylene rubber, red phosphorus and an antioxidant auxiliary agent into a pressurized internal mixer, controlling the maximum pressure of the internal mixer to be 3MPa, and mixing the components to 175 ℃ in the internal mixer to uniformly mix the components to obtain a mixed soft jelly;
the obtained mixed soft jelly is put into a double-screw extruder connected with a vacuum pump for extrusion, and 2, 5-dimethyl-2, 5-double-hexane is fed into a machine barrel through lateral feeding in a third zone, wherein the temperature of the double-screw extruder is as follows: 130-145 ℃ in the first area, 130-145 ℃ in the second area, 130-145 ℃ in the third area, 130-145 ℃ in the fourth area, 130-145 ℃ in the fifth area, 130-145 ℃ in the sixth area, 130-145 ℃ in the seventh area, 130-145 ℃ in the eighth area, 130-145 ℃ in the ninth area, 130-145 ℃ in the die head, 140-155 ℃ and the vacuum pump pressure is set to be 0.1-0.2 ATM;
through the process, the cable material extruded into particles can be obtained and packaged after air cooling.
Comparative example 1
Weighing the following components in percentage by mass:
10% of polyethylene, 13% of styrene-ethylene-butylene-styrene block copolymer, 12% of ethylene propylene rubber, 57% of magnesium hydroxide, 4% of red phosphorus, 1.2% of vinyl trisilane, 1.58% of antioxidant auxiliary agent, 1.2% of ethyl acetate and 0.02% of 2, 5-dimethyl-2, 5-bishexane.
Adding magnesium hydroxide into a high-speed mixer, setting the rotating speed of the high-speed mixer to 2000rpm and setting the temperature to 145 ℃; uniformly mixing vinyl trisilane and ethyl acetate, adding the mixture into a high-speed mixer through a nozzle at a speed of 200ml/min, simultaneously increasing the rotating speed of the high-speed mixer to 3000rpm, mixing for 8min, and completely removing the ethyl acetate serving as a diluent to obtain the treated halogen-free flame retardant;
adding the treated halogen-free flame retardant, polyethylene, styrene-ethylene-butylene-styrene segmented copolymer, ethylene propylene rubber, red phosphorus and an antioxidant auxiliary agent into a pressurized internal mixer, controlling the maximum pressure of the internal mixer to be 3MPa, and mixing the components to 175 ℃ in the internal mixer to uniformly mix the components to obtain a mixed soft jelly;
the obtained mixed soft jelly is put into a double-screw extruder connected with a vacuum pump for extrusion, and 2, 5-dimethyl-2, 5-double-hexane is fed into a machine barrel through lateral feeding in a third zone, wherein the temperature of the double-screw extruder is as follows: 130-145 ℃ in the first area, 130-145 ℃ in the second area, 130-145 ℃ in the third area, 130-145 ℃ in the fourth area, 130-145 ℃ in the fifth area, 130-145 ℃ in the sixth area, 130-145 ℃ in the seventh area, 130-145 ℃ in the eighth area, 130-145 ℃ in the ninth area, 130-145 ℃ in the die head, 140-155 ℃ and the vacuum pump pressure is set to be 0.1-0.2 ATM;
through the process, the cable material extruded into particles can be obtained and packaged after air cooling.
Comparative example 2
Weighing the following components in percentage by mass:
10% of polyethylene, 13% of styrene-ethylene-butylene-styrene block copolymer, 12% of ethylene propylene rubber, 57% of aluminum hydroxide, 4% of red phosphorus, 1.2% of tridecyl alcohol polyoxyethylene ether phosphate, 1.58% of antioxidant auxiliary agent, 1.2% of ethyl acetate and 0.02% of 2, 5-dimethyl-2, 5-bishexane.
Adding aluminum hydroxide into a high-speed mixer, setting the rotating speed of the high-speed mixer to 2000rpm and setting the temperature to 145 ℃; uniformly mixing tridecyl alcohol polyoxyethylene ether phosphate and ethyl acetate, adding the mixture into a high-speed mixer at a speed of 200ml/min through a nozzle, simultaneously increasing the rotating speed of the high-speed mixer to 3000rpm, mixing for 8min, and completely removing the ethyl acetate serving as a diluent to obtain the treated halogen-free flame retardant;
adding the treated halogen-free flame retardant, polyethylene, styrene-ethylene-butylene-styrene segmented copolymer, ethylene propylene rubber, red phosphorus and an antioxidant auxiliary agent into a pressurized internal mixer, controlling the maximum pressure of the internal mixer to be 3MPa, and mixing the components to 175 ℃ in the internal mixer to uniformly mix the components to obtain a mixed soft jelly;
the obtained mixed soft jelly is put into a double-screw extruder connected with a vacuum pump for extrusion, and 2, 5-dimethyl-2, 5-double-hexane is fed into a machine barrel through lateral feeding in a third zone, wherein the temperature of the double-screw extruder is as follows: 130-145 ℃ in the first area, 130-145 ℃ in the second area, 130-145 ℃ in the third area, 130-145 ℃ in the fourth area, 130-145 ℃ in the fifth area, 130-145 ℃ in the sixth area, 130-145 ℃ in the seventh area, 130-145 ℃ in the eighth area, 130-145 ℃ in the ninth area, 130-145 ℃ in the die head, 140-155 ℃ and the vacuum pump pressure is set to be 0.1-0.2 ATM;
through the process, the cable material extruded into particles can be obtained and packaged after air cooling.
Comparative example 3
Weighing the following components in percentage by mass:
10% of polyethylene, 13% of styrene-ethylene-butylene-styrene block copolymer, 12% of ethylene propylene rubber, 57% of magnesium hydroxide, 4% of red phosphorus, 1.2% of tridecyl alcohol polyoxyethylene ether phosphate, 1.58% of antioxidant auxiliary agent, 1.2% of ethyl acetate and 0.02% of 2, 5-dimethyl-2, 5-bishexane.
Adding magnesium hydroxide into a high-speed mixer, setting the rotating speed of the high-speed mixer to 2000rpm and setting the temperature to 145 ℃; uniformly mixing tridecyl alcohol polyoxyethylene ether phosphate and ethyl acetate, adding the mixture into a high-speed mixer at a speed of 200ml/min through a nozzle, simultaneously increasing the rotating speed of the high-speed mixer to 3000rpm, mixing for 8min, and completely removing the ethyl acetate serving as a diluent to obtain the treated halogen-free flame retardant;
putting the treated halogen-free flame retardant, polyethylene, styrene-ethylene-butylene-styrene segmented copolymer, ethylene propylene rubber, red phosphorus, an antioxidant auxiliary agent and two and five of the treated halogen-free flame retardant, polyethylene, styrene-ethylene-butylene-styrene segmented copolymer and the red phosphorus into a pressurized internal mixer, controlling the maximum pressure of the internal mixer to be 3MPa, and mixing the treated halogen-free flame retardant, the polyethylene, the styrene-ethylene-butylene-styrene segmented copolymer, the ethylene propylene rubber, the red phosphorus, the antioxidant auxiliary agent and the two and five of the treated red phosphorus into the internal mixer to be heated to 175 ℃ to uniformly mix the components in the internal mixer to obtain a mixed soft jelly;
putting the obtained mixed soft jelly into a double-screw extruder connected with a vacuum pump for extrusion, wherein the temperature of the double-screw extruder is as follows: 130-145 ℃ in the first area, 130-145 ℃ in the second area, 130-145 ℃ in the third area, 130-145 ℃ in the fourth area, 130-145 ℃ in the fifth area, 130-145 ℃ in the sixth area, 130-145 ℃ in the seventh area, 130-145 ℃ in the eighth area, 130-145 ℃ in the ninth area, 130-145 ℃ in the die head, 140-155 ℃ and the vacuum pump pressure is set to be 0.1-0.2 ATM;
through the process, the cable material extruded into particles can be obtained and packaged after air cooling.
Example 4
In this example, performance measurements were performed on the cable materials prepared in examples 1 to 3 and comparative examples 1 to 3, and on the commercial communication cable insulation cable material (hereinafter referred to as "a cable material") and the commercial low smoke halogen-free flame retardant cable material (hereinafter referred to as "B cable material"), the test methods were shown in table 1, table 2 shows the performance test results of the cable materials prepared in examples 1 to 3, and the performance test results of the cable materials a and B cable materials, and table 3 shows the performance test results of the cable materials prepared in comparative examples 1 to 3:
table 1 Cable material Performance test method
Test item Test method
Tensile Strength/MPa IEC 60811
Elongation at break/% IEC 60811
Volume resistivity at 20 ℃ per ohm cm IEC 60167
Dielectric constant GB/T 1409
Dielectric loss factor GB/T 1409
Combustion test/V0 UL94
Oxygen index/% ISO 4589-2
TABLE 2 detection results of Cable Material and A Cable Material and B Cable Material items prepared in examples 1 to 3
As shown in Table 2, three indexes (1) to (3) are compared, and the three indexes of volume resistivity, dielectric constant and dielectric loss factor of the commercial low-smoke halogen-free flame-retardant cable material are obviously lower than those of the cable materials prepared in examples 1 to 3.
As can be seen from the two indexes (4) and (5), the commercial communication cable insulating material has no flame retardant effect, so that when a fire disaster happens, the cable is quickly burnt out, the communication function is lost, and meanwhile, the flame quickly spreads and ignites surrounding objects; the cable material prepared by the embodiment has a good flame retardant effect, so that normal communication of the cable can be ensured in a short time when a fire disaster occurs, and the cable material has certain self-extinguishing performance and slows down the spread of the fire disaster.
The index (6) simulates the long-term working condition of the cable at the high temperature of the machine room. According to the index, the products prepared by the embodiments have no obvious degradation of various performances after aging, the retention rate of tensile strength and elongation at break is not less than 75%, the change rate of dielectric constant is not more than +/-25%, and the change rate of dielectric loss factor is not more than +/-25%, which indicates that the embodiments 1-3 can meet the long-term high-temperature use of the communication cable.
The index (7) simulates the long-term working condition of the cable under the working condition of high temperature and high humidity. From this index, it can be seen that the product prepared in the examples showed no significant deterioration in various properties after soaking in hot water. The retention rate of tensile strength and elongation at break is more than or equal to 75%, the change rate of dielectric constant is not more than +/-25%, and the change rate of dielectric loss factor is not more than +/-25%, which shows that the cable materials prepared in examples 1-3 can ensure long-term use of the communication cable under high-temperature and high-humidity conditions; compared with the commercial low-smoke halogen-free flame-retardant cable material, the dielectric constant change rate of the cable material is +63.81%, the dielectric loss factor change rate of the cable material is +913.63%, and the change rate can cause serious signal attenuation of the cable, so that the cable prepared from the commercial low-smoke halogen-free flame-retardant cable material cannot be normally used at all under the conditions of high temperature and high humidity.
Table 3 results of testing various properties of the cable compositions prepared in comparative examples 1 to 3
According to the application, the surface treatment agent with very low polarity, namely tridecyl alcohol polyoxyethylene ether phosphate, is selected to modify the halogen-free flame retardant, so that the compatibility of the flame retardant and the base material resin can be enhanced, and the polarity of the halogen-free flame retardant can be reduced; meanwhile, the ethyl acetate is used as a diluent, so that the tridecyl alcohol polyoxyethylene ether phosphate serving as a surface treatment agent can be coated on the surface of the flame retardant more uniformly, and can be fully removed after being mixed in a high-temperature high-speed mixer for a certain time, and the material performance is not affected.
When the material is extruded by the double screw, the second section injects the second and the fifth into the machine barrel by the micro metering pump, because the reactivity of the second and the fifth at high temperature is very high, if the second and the fifth react with the resin directly in the banburying kettle, air can be in direct contact with high-temperature rubber compound, so that oxygen in the air can react with free radicals generated by double-five decomposition, the double-five utilization rate is incomplete, and further fluctuation of physical and chemical properties of materials is caused.
In conclusion, the low dielectric loss halogen-free flame-retardant cable material product prepared by the application has the characteristics of smooth appearance, excellent flame retardance, low polarization loss and low free loss. The flame-retardant cable has the remarkable advantages of good flame retardant property, reduced signal attenuation, long transmission distance and the like when transmitting high-frequency signals.
It should be noted that the above embodiments are only for illustrating the technical solution of the present application and not for limiting the same, and although the present application has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present application may be modified or substituted without departing from the spirit and scope of the technical solution of the present application, which is intended to be covered in the scope of the claims of the present application.

Claims (3)

1. A low dielectric loss halogen-free flame-retardant cable material is characterized in that: the weight percentages of the components are as follows: 8-15% of polyethylene, 10-15% of styrene-ethylene-butylene-styrene block copolymer, 10-15% of ethylene propylene rubber, 45-60% of halogen-free flame retardant, 1-4% of red phosphorus, 1-2% of surface treatment agent, 1-3% of antioxidant auxiliary agent, 1-2% of diluent, 0.01-0.05% of 2, 5-dimethyl-2, 5-bishexane, and the sum of the mass percentages of the components is 100%;
wherein the surface treatment agent is tridecyl alcohol polyoxyethylene ether phosphate, the diluent is ethyl acetate, the purity is more than or equal to 98%, the halogen-free flame retardant is magnesium hydroxide, and the purity is more than or equal to 99.5%;
the preparation method of the cable material comprises the following steps of,
adding the halogen-free flame retardant into a high-speed mixer, adding the mixed surface treatment agent and diluent into the high-speed mixer through a nozzle, and mixing until the diluent is completely discharged, thus obtaining the treated halogen-free flame retardant;
adding the treated halogen-free flame retardant, polyethylene, styrene-ethylene-butylene-styrene block copolymer, ethylene propylene rubber, red phosphorus and an antioxidant auxiliary agent into a pressurized internal mixer, and mixing to obtain a soft jelly;
putting the obtained jelly into a double-screw extruder, introducing a vacuum pump, wherein the temperature of a first area is 130-145 ℃, the temperature of a second area is 130-145 ℃, the temperature of a third area is 130-145 ℃, the temperature of a fourth area is 130-145 ℃, the temperature of a fifth area is 130-145 ℃, the temperature of a sixth area is 130-145 ℃, the temperature of a seventh area is 130-145 ℃, the temperature of an eighth area is 130-145 ℃, the temperature of a ninth area is 130-145 ℃, the temperature of a die head is 140-155 ℃, setting the pressure of the vacuum pump to 0.1-0.2 ATM, feeding 2, 5-dimethyl-2, 5-dioxane into a machine barrel in the third area through lateral feeding in the process, extruding to obtain a granular cable material, and packaging after air cooling.
2. The low dielectric loss halogen-free flame retardant cable material of claim 1, wherein: the density of the styrene-ethylene-butylene-styrene block copolymer is 0.910g/cm 3 Styrene content 33%; the density of the ethylene propylene rubber is 0.87. 0.87g/cm 3 Wherein the mass percentage of ethylene is 70%.
3. The low dielectric loss halogen-free flame retardant cable material of claim 1, wherein: the antioxidant auxiliary agent is prepared by mixing disulfide and tetra-4, 4-diphenyl diphosphite together according to the mass ratio of 1:1.
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