CN112812420B - Low-smoke halogen-free cable material containing functional compatilizer and preparation thereof - Google Patents

Low-smoke halogen-free cable material containing functional compatilizer and preparation thereof Download PDF

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CN112812420B
CN112812420B CN202110139222.1A CN202110139222A CN112812420B CN 112812420 B CN112812420 B CN 112812420B CN 202110139222 A CN202110139222 A CN 202110139222A CN 112812420 B CN112812420 B CN 112812420B
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compatilizer
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cable material
halogen
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CN112812420A (en
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崔曾涛
崔增波
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Langfang Cui's Cable Materials Co ltd
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Langfang Cui's Cable Materials 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
    • 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
    • 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
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • 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
    • C08L2205/03—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
    • 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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  • Chemical Kinetics & Catalysis (AREA)
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  • Organic Insulating Materials (AREA)
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Abstract

The invention relates to a low-smoke halogen-free cable material containing a functional compatilizer and a preparation method thereof, wherein the cable material is prepared from the following raw materials in parts by weight: 50-60 parts of ethylene-vinyl acetate copolymer, 20-40 parts of fluorosilicone rubber, 10-20 parts of terpene resin, 15-30 parts of polyphenyl ether resin, 6-15 parts of functional compatilizer, 50-70 parts of halogen-free flame retardant, 5-10 parts of reinforcing agent, 2-6 parts of peroxide cross-linking agent, 3-9 parts of stabilizer, 0.5-1 part of lubricant and 0.2-1 part of antioxidant. Compared with the prior art, the cable material disclosed by the invention is simple in preparation process, has good molding processability and physical and mechanical properties, is resistant to oil stain, heat, cold, aging, water, acid and alkali, and chemical reagents, has excellent electrical insulation and heat-resistant flame retardance, ensures the working performance and service life of the cable, greatly improves the safety and reliability of the cable in use, and can realize industrial production.

Description

Low-smoke halogen-free cable material containing functional compatilizer and preparation thereof
Technical Field
The invention belongs to the technical field of wires and cables, and relates to a low-smoke halogen-free cable material containing a functional compatilizer and a preparation method thereof.
Background
With the rapid development of economic construction, the living standard of people is continuously improved, and the demand of various cables is increased due to the rapid development of various infrastructures in cities and countryside. The cable is a carrier of power transmission, is the basis of guaranteeing the normal work of electric products, plays the effect of transmitting electric power, transmitting information and realizing electromagnetic energy conversion in electric products. The cable material is a necessary material for preparing the cable, and the performance of the cable material directly influences the transmission quality of various energies and signals and the service life of the cable.
The existing conventional cable material on the market has poor weather resistance, when equipment works outdoors or is always placed in the atmosphere for long-term irradiation of solar ultraviolet rays, the surface of the cable material is cracked, and the connecting wires of some equipment or automobiles are in direct contact with mineral oil such as gasoline, engine oil and the like, so that the surface swelling phenomenon is easy to occur, and the physical and mechanical properties of the cable material are greatly reduced. The cable materials have more potential risks in the use process, and directly influence the property safety and the personal safety of electronic and electrical equipment, automobiles and the like. Especially, the short circuit of the cable in some large-scale electronic and electric equipment is easy to burn out the electric equipment, and fire can happen in serious conditions. When the working environment is high, the phenomena of melting, dry cracking and the like can occur, the insulating function is lost, the cable becomes soft under the long-time high-power use state, and the mechanical property is poor. In addition, in the practical application process, the electric wire and the electric cable can be bent along with the movement of the electric wire and the electric cable, the electric wire and the electric cable are frequently inserted and pulled out, the electric wire and the electric cable are not good in flexibility and can be broken when being used for a long time, and the phenomenon is more obvious particularly in a high-temperature working occasion.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a low-smoke halogen-free cable material containing a functional compatilizer, which is convenient to form and process, better in weather resistance, water erosion resistance, flame retardance, high-temperature resistance and environmental protection performance and longer in service life, and a preparation method thereof.
The purpose of the invention can be realized by the following technical scheme:
according to one aspect of the invention, the low-smoke halogen-free cable material containing the functional compatilizer is prepared from the following raw materials in parts by weight: 50-60 parts of ethylene-vinyl acetate copolymer, 20-40 parts of fluorosilicone rubber, 10-20 parts of terpene resin, 15-30 parts of polyphenyl ether resin, 6-15 parts of functional compatilizer, 50-70 parts of halogen-free flame retardant, 5-10 parts of reinforcing agent, 2-6 parts of peroxide cross-linking agent, 3-9 parts of stabilizer, 0.5-1 part of lubricant and 0.2-1 part of antioxidant.
In one embodiment, the ethylene-vinyl acetate copolymer has a vinyl acetate content of 12 to 25wt% and a melt index of 8 to 20 g/10min (190 ℃,2.16 kg).
As an embodiment, the fluorosilicone rubber has a reduction rate of not more than 35% in tensile strength at 225 ℃ for 72 hours from its initial tensile strength and a reduction rate of not more than 30% in elongation at break from its initial elongation at break.
Preferably, the fluorosilicone rubber may be selected from the group consisting of FSR8430-U, FSR8440-U, FSR8460-U, FSR8470-U, which are commercially available.
In one embodiment, the terpene resin has a softening point of 100-130 deg.C and an acid value less than 1.0 mg KOH/g.
Preferably, the terpene resin may be selected from one or more of commercially available TP1105, TP1115 or TP 1125.
In one embodiment, the polyphenylene ether resin has a molding shrinkage of 0.7% or less and a volume resistivity of 1000 Ω & cm or more at 23 ℃ and a relative humidity of 50%.
Preferably, the polyphenylene ether resin is available from 540Z, manufactured by asahi.
As an embodiment, the functional compatilizer is prepared by compounding the following components in parts by weight: 70-90 parts of maleic anhydride grafted hydrogenated styrene-butadiene-styrene block copolymer, 10-30 parts of siloxane copolymer, 15-30 parts of modified kaolin and 2-8 parts of alicyclic amine activator.
As an embodiment, the modified kaolin is prepared by the following steps: mixing kaolin powder and absolute ethyl alcohol uniformly to prepare a mixed solution of the kaolin powder and the absolute ethyl alcohol; adding hydroxymethyl cellulose, a silane coupling agent and calcium sulfate whiskers into the mixed solution, adjusting the pH of the solution to 5 by using dilute nitric acid, reacting for 2-4 hours at 60-72 ℃, cooling, filtering, washing, drying to constant weight, grinding, and sieving with a 1000-mesh sieve.
Preferably, the kaolin powder and the absolute ethyl alcohol are in the following dosage relationship: every 100 mL of absolute ethyl alcohol is added with 10-20 g of kaolin powder, the dosage of the hydroxymethyl cellulose is 10-15% of the mass of the kaolin powder, the dosage of the silane coupling agent is 2-5% of the mass of the kaolin powder, and the dosage of the calcium sulfate whisker is 1-3% of the mass of the kaolin powder.
Preferably, the maleic anhydride grafted hydrogenated styrene-butadiene-styrene block copolymer is available from Kraton FG 1901, shell company, usa.
Preferably, the siloxane copolymer is selected from one or more of polyimide siloxane, polyetherimide sulfone siloxane, polysulfone siloxane, polyether sulfone siloxane or polyphenylene ether siloxane.
Preferably, the alicyclic amine activator is selected from triethylenediamine, hexamethylenetetramine or diethylenetriamine.
The functional compatilizer can be prepared by the following method: adding the raw material components into a double-screw extruder according to the parts by weight, extruding at 230-250 ℃, and granulating.
As an embodiment, the halogen-free flame retardant is a phosphorus-containing flame retardant, and may be selected from one or more of triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, ditolyl phosphate, tris (2, 4, 6-trimethylphenyl) phosphate, tris (2, 4-di-t-butylphenyl) phosphate, tris (2, 6-di-t-butylphenyl) phosphate, resorcinol bis (diphenyl phosphate), hydroquinone bis (diphenyl phosphate), bisphenol A-bis (diphenyl phosphate), resorcinol bis (2, 6-di-t-butylphenyl phosphate), hydroquinone bis (2, 6-dimethylphenyl phosphate).
As an embodiment, the reinforcing agent is fumed silica.
As an embodiment, the peroxide crosslinking agent is selected from one or more of bis (4-methylbenzoyl) peroxide, tert-butyl peroxy-2-ethylhexyl carbonate or 1, 1-bis (tert-butyl peroxy) cyclohexane.
In one embodiment, the stabilizer is an organotin-based heat stabilizer and may be selected from at least one of dibutyltin maleate, dibutyltin dilaurate, dibutyltin laurate maleate, di-n-octyltin dilaurate, or di-n-octyltin bis (isooctyl thioglycolate).
As an embodiment, the lubricant is at least one of natural paraffin, liquid paraffin, microcrystalline paraffin, polyethylene wax, butyl stearate, oleamide, ethylene bis stearamide or silicone powder.
As an embodiment, the antioxidant is at least one of 2, 6-di-t-butyl-p-cresol, octadecyl beta (3, 5-di-t-butyl-4-hydroxyphenyl) propionate, 1,3 tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 2' -methylenebis (4-ethyl-6-t-butylphenol), 1,3, 5-tris (3, 5-t-butyl-4-hydroxybenzyl) trimethylbenzene, 2' -methylenebis (4-methyl-6-t-butylphenol), 4' -di-t-octyldiphenylamine.
According to another aspect of the present invention, there is provided a preparation method of the low smoke zero halogen cable material containing the functional compatibilizer, which includes the following steps:
step 1): uniformly stirring and mixing ethylene-vinyl acetate copolymer, polyphenyl ether resin, a functional compatilizer, a halogen-free flame retardant, a peroxide crosslinking agent, a stabilizer, a lubricant and an antioxidant in parts by weight at a high speed to prepare a premix A;
step 2): uniformly stirring and mixing the fluorosilicone rubber, the terpene resin and the reinforcing agent at a high speed according to the parts by weight to prepare a premix B;
and step 3): adding the premix A into a double-screw extruder from a main feed inlet, adding the premix B into the double-screw extruder through a side feed inlet, and cooling, drying and granulating after extrusion to obtain the low-smoke halogen-free cable material.
As a preferred technical scheme, the temperature of a first zone of the double-screw extruder is 210-230 ℃, the temperature of a second zone is 220-240 ℃, the temperature of a third zone is 220-240 ℃, the temperature of a fourth zone is 220-240 ℃, the temperature of a fifth zone is 230-250 ℃, the temperature of a sixth zone is 240-260 ℃, the temperature of a seventh zone is 230-250 ℃, the temperature of an eighth zone is 220-240 ℃ and the temperature of a ninth zone is 200-220 ℃.
Compared with the prior art, the invention has the following characteristics:
1) The cable material disclosed by the invention takes the ethylene-vinyl acetate copolymer as a main base material, the fluorosilicone rubber is introduced to enhance the toughness and weather aging resistance of the base material, the fluorosilicone rubber carries a fluorine-containing group, the medium resistance of the base material is favorably improved, the tolerance of a material system to organic solvents, oil substances and acid and alkali substances can be improved, in addition, aiming at the fluorosilicone rubber, the molecular main chain structural unit of the fluorosilicone rubber is-Si-O-, the fumed silica is taken as a reinforcing agent as an auxiliary, the fluorosilicone rubber and the air-phase silica have the same silica framework, the air-phase silica particles can be stably filled in gaps of a cross-linking network in the fluorosilicone rubber, so that a stronger interaction is formed, the strength of the fluorosilicone rubber can be enhanced, the fluorosilicone rubber can be taken as a carrier and dispersed in the ethylene-vinyl acetate copolymer base material, the heat resistance and the electrical resistivity of the base material can be effectively improved, the final material has excellent electric flame retardance and aging resistance, and the terpene resin is compounded with the fluorosilicone rubber, the adhesion between the fluorosilicone rubber particles and the base material can be stably fused in the base material, and the aging resistance of the base material can be further improved;
2) The polyphenyl ether resin is introduced into a material system, the electrical insulation of a base material can be further improved, the wear resistance and the size stability of a final material system are favorably improved, the polyphenyl ether resin has self-extinguishing property and can endow the base material with safer flame retardance, and in order to improve the compatibility between the polyphenyl ether resin, the fluorosilicone rubber and the base material, the functional compatilizer adopted by the invention is prepared by adopting maleic anhydride grafted hydrogenated styrene-butadiene-styrene block copolymer, siloxane copolymer, modified kaolin and alicyclic amine activating agent through extrusion granulation, wherein the modified kaolin is prepared by adopting silane coupling agent to graft hydroxymethyl cellulose onto the surface of kaolin particles, the modified kaolin particles can form stronger chemical bonds with the maleic anhydride grafted hydrogenated styrene-butadiene-styrene block copolymer and the siloxane copolymer under the action of the alicyclic amine activator, so that a cross-linked network is formed between the maleic anhydride grafted hydrogenated styrene-butadiene-styrene block copolymer and the siloxane copolymer, and the maleic anhydride grafted hydrogenated styrene-butadiene-styrene block copolymer and the siloxane copolymer can be stably combined together to form a composite carrier, thereby being beneficial to reducing the size of dispersed particles of the modified kaolin to uniformly and stably disperse the dispersed particles in base resin, improving the volume resistivity and the heat-resistant flame retardance of a material system, reducing the interfacial tension between the ethylene-vinyl acetate copolymer, the fluorosilicone rubber and the polyphenyl ether resin, increasing the compatibility of the three, uniformly stabilizing the dispersed phase and the continuous phase, and improving the processing rheological property of the material system;
3) The cable material disclosed by the invention is simple in preparation process, has good molding processability and physical and mechanical properties, is resistant to oil stain, heat, cold, aging, water, acid and alkali, and chemical reagents, has excellent electrical insulation and heat-resistant flame retardance, ensures the working performance and the service life of the cable, greatly improves the safety and the reliability of the cable in use, and can realize industrial production.
Detailed Description
The technical solutions of the present invention will be described below clearly and completely in connection with specific embodiments, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, not all of the embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed embodiment and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments. All other embodiments obtained by a person skilled in the art without making any inventive step are within the scope of protection of the present invention.
As used herein, the term "about" when used to modify a numerical value means within 5% of the error margin measured for that value.
The theory or mechanism described and disclosed herein, whether correct or incorrect, should not limit the scope of the present invention in any way, i.e., the present disclosure may be practiced without limitation to any particular theory or mechanism.
The present invention will be described in detail with reference to specific examples.
Example 1:
the low-smoke halogen-free cable material is prepared from the following raw materials in parts by weight: 50 parts of ethylene-vinyl acetate copolymer, 20 parts of fluorosilicone rubber, 10 parts of terpene resin, 15 parts of polyphenyl ether resin, 6 parts of functional compatilizer, 50 parts of halogen-free flame retardant, 5 parts of reinforcing agent, 2 parts of peroxide cross-linking agent, 3 parts of stabilizer, 0.5 part of lubricant and 0.2 part of antioxidant.
Wherein the ethylene-vinyl acetate copolymer has a vinyl acetate content of 12 wt% and a melt index of about 8 g/10min (190 deg.C, 2.16 kg); the fluorosilicone rubber used is FSR8430-U sold in the market; the terpene resin used was commercially available TP1105; the polyphenylene ether resin has a molding shrinkage of 0.7% or less, a volume resistivity of 1000 Ω -cm at 23 deg.C and 50% relative humidity, and is available from 540Z of Asahi chemical; the halogen-free flame retardant is triphenyl phosphate; the reinforcing agent is fumed silica; the peroxide crosslinking agent is di (4-methylbenzoyl) peroxide; the stabilizer is dibutyltin maleate; the used lubricant is natural paraffin; the antioxidant is prepared by mixing 2, 6-di-tert-butyl-p-cresol and 4,4' -di-tert-octyldiphenylamine according to a mass ratio of 4.
The functional compatilizer in the embodiment is prepared by compounding the following components in parts by weight: 70 parts of maleic anhydride grafted hydrogenated styrene-butadiene-styrene block copolymer, 10 parts of siloxane copolymer, 15 parts of modified kaolin and 2 parts of alicyclic amine activator; of these, the maleic anhydride grafted hydrogenated styrene-butadiene-styrene block copolymer was obtained from Kraton FG 1901, shell, usa, and the siloxane copolymer was a polyimide siloxane and the alicyclic amine activator was triethylenediamine.
The preparation method of the modified kaolin used in the functional compatilizer comprises the following steps: mixing kaolin powder and absolute ethyl alcohol uniformly to prepare a mixed solution of the kaolin powder and the absolute ethyl alcohol; adding hydroxymethyl cellulose, a silane coupling agent and calcium sulfate whiskers into the mixed solution, adjusting the pH of the solution to 5 by using dilute nitric acid, reacting for 4 hours at 60 ℃, cooling, filtering, washing, drying to constant weight, grinding, and sieving with a 1000-mesh sieve.
In the preparation method, the dosage relationship between the kaolin powder and the absolute ethyl alcohol is as follows: every 100 mL of absolute ethyl alcohol is added with 10 g of kaolin powder, the dosage of hydroxymethyl cellulose is 10 percent of the mass of the kaolin powder, the dosage of silane coupling agent is 2 percent of the mass of the kaolin powder, and the dosage of calcium sulfate whisker is 1 percent of the mass of the kaolin powder.
Based on the raw materials of each component of the functional compatilizer, the raw materials are added into a double-screw extruder according to the parts by weight, and are extruded and granulated at 230 ℃ to obtain the functional compatilizer.
Example 2:
the low-smoke halogen-free cable material is prepared from the following raw materials in parts by weight: 60 parts of ethylene-vinyl acetate copolymer, 40 parts of fluorosilicone rubber, 20 parts of terpene resin, 30 parts of polyphenyl ether resin, 15 parts of functional compatilizer, 70 parts of halogen-free flame retardant, 10 parts of reinforcing agent, 6 parts of peroxide cross-linking agent, 9 parts of stabilizer, 1 part of lubricant and 1 part of antioxidant.
Wherein the ethylene-vinyl acetate copolymer used has a vinyl acetate content of 25wt% and a melt index of about 20 g/10min (190 ℃,2.16 kg); the fluorosilicone rubber used is FSR8440-U which is commercially available; the terpene resin used was commercially available TP1115; the polyphenylene ether resin has a molding shrinkage of 0.7% or less, a volume resistivity of 1000 Ω -cm at 23 deg.C and 50% relative humidity, and is available from 540Z available from Asahi Kasei K.K.; the used halogen-free flame retardant is formed by mixing cresyl diphenyl phosphate and tri (2, 4, 6-trimethylphenyl) phosphate according to the mass ratio of 1; the reinforcing agent is fumed silica; the peroxide crosslinking agent is di (4-methylbenzoyl) peroxide; the stabilizer used is dibutyltin dilaurate; the lubricant used was butyl stearate; the antioxidant used was octadecyl beta (3, 5 di-tert-butyl-4-hydroxyphenyl) propionate.
The functional compatilizer in the embodiment is prepared by compounding the following components in parts by weight: 90 parts of maleic anhydride grafted hydrogenated styrene-butadiene-styrene block copolymer, 30 parts of siloxane copolymer, 30 parts of modified kaolin and 8 parts of alicyclic amine activator; among them, maleic anhydride grafted hydrogenated styrene-butadiene-styrene block copolymer was purchased from Kraton FG 1901, shell company, usa, the siloxane copolymer was polyetherimide siloxane, and the alicyclic amine activator was hexamethylenetetramine.
The preparation method of the modified kaolin used in the functional compatilizer comprises the following steps: mixing kaolin powder and absolute ethyl alcohol uniformly to prepare a mixed solution of the kaolin powder and the absolute ethyl alcohol; adding hydroxymethyl cellulose, a silane coupling agent and calcium sulfate whiskers into the mixed solution, adjusting the pH of the solution to 5 by using dilute nitric acid, reacting for 2 hours at 72 ℃, cooling, filtering, washing, drying to constant weight, grinding, and sieving with a 1000-mesh sieve.
In the preparation method, the dosage relationship between the kaolin powder and the absolute ethyl alcohol is as follows: every 100 mL of absolute ethyl alcohol is added with 20 g of kaolin powder, the dosage of hydroxymethyl cellulose is 15 percent of the mass of the kaolin powder, the dosage of silane coupling agent is 5 percent of the mass of the kaolin powder, and the dosage of calcium sulfate whisker is 3 percent of the mass of the kaolin powder.
Based on the raw materials of each component of the functional compatilizer, the raw materials are added into a double-screw extruder according to the parts by weight, and are extruded and granulated at 250 ℃ to obtain the functional compatilizer.
Example 3:
the low-smoke halogen-free cable material is prepared from the following raw materials in parts by weight: 54 parts of ethylene-vinyl acetate copolymer, 32 parts of fluorosilicone rubber, 14 parts of terpene resin, 20 parts of polyphenyl ether resin, 10 parts of functional compatilizer, 56 parts of halogen-free flame retardant, 6 parts of reinforcing agent, 4 parts of peroxide cross-linking agent, 4 parts of stabilizer, 0.6 part of lubricant and 0.4 part of antioxidant.
Wherein the ethylene-vinyl acetate copolymer has a vinyl acetate content of 18 wt% and a melt index of about 11 g/10min (190 deg.C, 2.16 kg); the fluorosilicone rubber used is FSR8460-U which is sold on the market; the terpene resin used was commercially available TP1125; the polyphenylene ether resin has a molding shrinkage of 0.7% or less, a volume resistivity of 1000 Ω -cm at 23 deg.C and 50% relative humidity, and is available from 540Z of Asahi chemical; the halogen-free flame retardant is hydroquinone bis (2, 6-dimethylphenyl phosphate); the reinforcing agent is fumed silica; the peroxide crosslinking agent is tert-butyl peroxy-2-ethylhexyl carbonate; the stabilizer is prepared by mixing dibutyltin laurate maleate and di (isooctyl thioglycolate) di-n-octyltin according to the mass ratio of 9; the lubricant is prepared by mixing natural paraffin, polyethylene wax and ethylene bis stearamide according to a mass ratio of 1; the antioxidant used was 2,2' -methylenebis (4-methyl-6-tert-butylphenol).
The functional compatilizer in the embodiment is prepared by compounding the following components in parts by weight: 82 parts of maleic anhydride grafted hydrogenated styrene-butadiene-styrene block copolymer, 18 parts of siloxane copolymer, 25 parts of modified kaolin and 5 parts of alicyclic amine activator; the maleic anhydride grafted hydrogenated styrene-butadiene-styrene block copolymer is obtained from Kraton FG 1901 of Shell company of America, the siloxane copolymer is polyetherimide sulfone siloxane, and the alicyclic amine activator is a mixture of hexamethylenetetramine and diethylenetriamine according to the mass ratio of 1.
The preparation method of the modified kaolin used in the functional compatilizer comprises the following steps: mixing kaolin powder and absolute ethyl alcohol uniformly to prepare a mixed solution of the kaolin powder and the absolute ethyl alcohol; adding hydroxymethyl cellulose, a silane coupling agent and calcium sulfate whiskers into the mixed solution, adjusting the pH of the solution to 5 by using dilute nitric acid, reacting for 3 hours at 68 ℃, cooling, filtering, washing, drying to constant weight, grinding, and sieving by using a 1000-mesh sieve.
In the preparation method, the dosage relationship between the kaolin powder and the absolute ethyl alcohol is as follows: every 100 mL of absolute ethyl alcohol is added with 15 g of kaolin powder, the dosage of hydroxymethyl cellulose is 12 percent of the mass of the kaolin powder, the dosage of silane coupling agent is 4 percent of the mass of the kaolin powder, and the dosage of calcium sulfate whisker is 2 percent of the mass of the kaolin powder.
Based on the raw materials of each component of the functional compatilizer, the raw materials are added into a double-screw extruder according to the parts by weight, and the raw materials are extruded and granulated at 250 ℃ to obtain the functional compatilizer.
Example 4:
the low-smoke halogen-free cable material is prepared from the following raw materials in parts by weight: 58 parts of ethylene-vinyl acetate copolymer, 27 parts of fluorosilicone rubber, 12 parts of terpene resin, 23 parts of polyphenyl ether resin, 9 parts of functional compatilizer, 52 parts of halogen-free flame retardant, 7 parts of reinforcing agent, 4 parts of peroxide crosslinking agent, 8 parts of stabilizer, 0.7 part of lubricant and 0.8 part of antioxidant.
Wherein the ethylene-vinyl acetate copolymer used has a vinyl acetate content of 22 wt% and a melt index of about 18 g/10min (190 ℃,2.16 kg); the fluorosilicone rubber used is FSR8470-U sold in the market; the terpene resin used was commercially available TP1125; the polyphenylene ether resin has a molding shrinkage of 0.7% or less, a volume resistivity of 1000 Ω -cm at 23 deg.C and 50% relative humidity, and is available from 540Z available from Asahi Kasei K.K.; the used halogen-free flame retardant is resorcinol bis (2, 6-di-tert-butyl phenyl phosphate); the reinforcing agent is fumed silica; the peroxide crosslinking agent used is 1, 1-di (t-butylperoxy) cyclohexane; the stabilizer used is di-n-octyltin dilaurate; the lubricant is prepared by mixing microcrystalline paraffin, oleamide and silicone powder according to the mass ratio of 1; the antioxidant used was 1,3, 5-tris (3, 5-tert-butyl-4-hydroxybenzyl) trimethylbenzene.
The functional compatilizer in the embodiment is prepared by compounding the following components in parts by weight: 76 parts of maleic anhydride grafted hydrogenated styrene-butadiene-styrene block copolymer, 24 parts of siloxane copolymer, 26 parts of modified kaolin and 4 parts of alicyclic amine activator; the maleic anhydride grafted hydrogenated styrene-butadiene-styrene block copolymer is purchased from Kraton FG 1901 of Shell company of America, the siloxane copolymer is formed by mixing polyphenylene ether siloxane and polysulfone siloxane according to the mass ratio of 4.
The preparation method of the modified kaolin used in the functional compatilizer comprises the following steps: mixing kaolin powder and absolute ethyl alcohol uniformly to prepare a mixed solution of the kaolin powder and the absolute ethyl alcohol; adding hydroxymethyl cellulose, a silane coupling agent and calcium sulfate whiskers into the mixed solution, adjusting the pH of the solution to 5 by using dilute nitric acid, reacting for 4 hours at 65 ℃, cooling, filtering, washing, drying to constant weight, grinding, and sieving with a 1000-mesh sieve.
In the preparation method, the dosage relationship between the kaolin powder and the absolute ethyl alcohol is as follows: every 100 mL of absolute ethyl alcohol is added with 18 g of kaolin powder, the dosage of the hydroxymethyl cellulose is 14 percent of the mass of the kaolin powder, the dosage of the silane coupling agent is 5 percent of the mass of the kaolin powder, and the dosage of the calcium sulfate whisker is 2 percent of the mass of the kaolin powder.
Based on the raw materials of each component of the functional compatilizer, the raw materials are added into a double-screw extruder according to the parts by weight, and are extruded and granulated at 250 ℃ to obtain the functional compatilizer.
The cable materials of the above examples 1-4 were prepared by the following method:
step 1): uniformly stirring and mixing ethylene-vinyl acetate copolymer, polyphenyl ether resin, a functional compatilizer, a halogen-free flame retardant, a peroxide cross-linking agent, a stabilizer, a lubricant and an antioxidant in parts by weight at a high speed to prepare premix A;
step 2): uniformly stirring and mixing the fluorosilicone rubber, the terpene resin and the reinforcing agent at a high speed according to the parts by weight to prepare a premix B;
step 3): adding the premix A into a double-screw extruder from a main feed inlet, adding the premix B into the double-screw extruder through a side feed inlet, cooling, drying and granulating after extrusion to obtain the low-smoke halogen-free cable material.
In the preparation method, the temperature of the first zone of the double-screw extruder is 230 ℃, the temperature of the second zone is 235 ℃, the temperature of the third zone is 240 ℃, the temperature of the fourth zone is 240 ℃, the temperature of the fifth zone is 250 ℃, the temperature of the sixth zone is 260 ℃, the temperature of the seventh zone is 252 ℃, the temperature of the eighth zone is 240 ℃ and the temperature of the ninth zone is 220 ℃.
Comparative example 1:
the comparative example cable material was prepared as described in example 3 with Kraton FG 1901 as the compatibilizer.
Comparative example 2:
this comparative example does not contain fluorosilicone rubber, terpene resin, and reinforcing agent, as in example 3.
The results of the performance test of the cable materials prepared in examples 1 to 4 and comparative examples 1 to 2 are shown in table 1 below.
TABLE 1 test results
Figure 799542DEST_PATH_IMAGE001
Note: the tensile strength and elongation at break tests in Table 1 were carried out in accordance with GB/T1040.3.
As can be seen from the test results in Table 1, the cable materials prepared in the embodiments 1-4 of the present invention have the advantages of excellent mechanical strength, good water erosion resistance, outstanding flame retardancy and insulation property, and good application prospects.
Although the present invention has been described in detail, modifications within the spirit and scope of the invention will be apparent to those skilled in the art. Furthermore, it should be understood that the various aspects recited herein, portions of different embodiments, and various features listed may be combined or interchanged either in whole or in part. In the various embodiments described above, those embodiments that refer to another embodiment may be combined with other embodiments as appropriate, as will be appreciated by those skilled in the art. Furthermore, those skilled in the art will appreciate that the foregoing description is by way of example only, and is not intended to limit the invention.

Claims (7)

1. The low-smoke halogen-free cable material containing the functional compatilizer is characterized by being prepared from the following raw materials in parts by weight: 50-60 parts of ethylene-vinyl acetate copolymer, 20-40 parts of fluorosilicone rubber, 10-20 parts of terpene resin, 15-30 parts of polyphenyl ether resin, 6-15 parts of functional compatilizer, 50-70 parts of halogen-free flame retardant, 5-10 parts of reinforcing agent, 2-6 parts of peroxide cross-linking agent, 3-9 parts of stabilizer, 0.5-1 part of lubricant and 0.2-1 part of antioxidant;
the functional compatilizer is prepared by compounding the following components in parts by weight: 70-90 parts of maleic anhydride grafted hydrogenated styrene-butadiene-styrene block copolymer, 10-30 parts of siloxane copolymer, 15-30 parts of modified kaolin and 2-8 parts of alicyclic amine activator; the preparation method of the modified kaolin comprises the following steps: mixing kaolin powder and absolute ethyl alcohol uniformly to prepare a mixed solution of the kaolin powder and the absolute ethyl alcohol; adding hydroxymethyl cellulose, a silane coupling agent and calcium sulfate whiskers into the mixed solution, adjusting the pH of the solution to 5 by using dilute nitric acid, reacting for 2-4 hours at 60-72 ℃, cooling, filtering, washing, drying to constant weight, grinding, and sieving with a 1000-mesh sieve; the dosage relation of the kaolin powder and the absolute ethyl alcohol is as follows: 10-20 g of kaolin powder is added into each 100 mL of absolute ethyl alcohol, the dosage of the hydroxymethyl cellulose is 10-15% of the mass of the kaolin powder, the dosage of the silane coupling agent is 2-5% of the mass of the kaolin powder, and the dosage of the calcium sulfate whisker is 1-3% of the mass of the kaolin powder.
2. The low smoke zero halogen cable material containing the functional compatilizer according to claim 1, wherein the ethylene-vinyl acetate copolymer has a vinyl acetate content of 12-25wt% and a melt index of 8-20 g/10min (190 ℃,2.16 kg).
3. The low smoke zero halogen cable material containing the functional compatibilizer as claimed in claim 1, wherein a decrease rate of a tensile strength of the fluorosilicone rubber at 225 ℃ for 72 hours is not more than 35% from an initial tensile strength thereof, and a decrease rate of an elongation at break from an initial elongation at break thereof is not more than 30%.
4. The low-smoke halogen-free cable material containing the functional compatilizer as claimed in claim 1, wherein a molding shrinkage rate of the polyphenylene ether resin is not more than 0.7%, and a volume resistivity thereof is more than 1000 Ω -cm under conditions of 23 ℃ and a relative humidity of 50%.
5. The low smoke zero halogen cable material containing functional compatilizer according to claim 1, wherein the siloxane copolymer is selected from one or more of polyimide siloxane, polyetherimide sulfone siloxane, polysulfone siloxane, polyethersulfone siloxane or polyphenylene ether siloxane;
the alicyclic amine activator is selected from triethylenediamine, hexamethylenetetramine or diethylenetriamine.
6. The low smoke zero halogen cable material containing functional compatilizer according to claim 1, wherein the halogen-free flame retardant is phosphorus-containing flame retardant, the reinforcing agent is fumed silica, the peroxide crosslinking agent is one or more of bis (4-methylbenzoyl) peroxide, t-butylperoxy-2-ethylhexyl carbonate or 1, 1-bis (t-butylperoxy) cyclohexane, the stabilizer is an organic tin heat stabilizer, the lubricant is at least one of natural paraffin, liquid paraffin, microcrystalline paraffin, polyethylene wax, butyl stearate, oleamide, ethylene bis stearamide and silicone powder, and the antioxidant is at least one of 2, 6-di-t-butyl-p-cresol, octadecyl beta (3, 5-di-t-butyl-4-hydroxyphenyl) propionate, 1,3 tris (2-methyl-4 hydroxy-5 t-butylphenyl) butane, 2' -methylene bis (4-ethyl-6 t-butylphenol), 1,3, 5-tris (3, 5-t-butyl-4-hydroxybenzyl) trimethylbenzene, 2' -methyl bis (4-octyl-4-t-butylphenol) diphenylamine and 4' -di-t-butyl-octylphenol.
7. The method for preparing a low-smoke halogen-free cable material containing a functional compatilizer according to any one of claims 1 to 6, wherein the method comprises the following steps:
step 1): uniformly stirring and mixing ethylene-vinyl acetate copolymer, polyphenyl ether resin, a functional compatilizer, a halogen-free flame retardant, a peroxide crosslinking agent, a stabilizer, a lubricant and an antioxidant in parts by weight at a high speed to prepare a premix A;
step 2): uniformly stirring and mixing the fluorosilicone rubber, the terpene resin and the reinforcing agent at a high speed according to the parts by weight to prepare a premix B;
step 3): adding the premix A into a double-screw extruder from a main feed inlet, adding the premix B into the double-screw extruder through a side feed inlet, and cooling, drying and granulating after extrusion to obtain the low-smoke halogen-free cable material.
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