CN112795079A - Low-smoke halogen-free cable material containing novel capsule flame retardant and preparation method thereof - Google Patents
Low-smoke halogen-free cable material containing novel capsule flame retardant and preparation method thereof Download PDFInfo
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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
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Abstract
The invention relates to a low-smoke halogen-free cable material containing a novel capsule flame retardant and a preparation method thereof, wherein the cable material is prepared from the following raw materials in parts by weight: 40-60 parts of ethylene-vinyl acetate copolymer, 20-40 parts of fluorosilicone rubber, 10-20 parts of terpene resin, 20-30 parts of metallocene polyethylene, 25-40 parts of capsule flame retardant, 15-25 parts of compatilizer, 5-10 parts of reinforcing agent, 3-9 parts of stabilizer, 0.3-0.8 part of peroxide cross-linking agent, 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, good in molding processability, oil stain resistance, good in weather resistance, outstanding in flame-retardant and smoke-suppression effects, good in mechanical strength and toughness, capable of ensuring the working performance and service life of the cable and greatly improving the safety and reliability of the cable in use.
Description
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 novel capsule flame retardant and a preparation method thereof.
Background
The cable is an important conductive device of a power system, plays a role in transmitting electric energy, and is mainly used for electric energy transmission of a generator, a transformer, a motor and the like, at present, electric equipment such as high-low voltage power distribution of a substation, a motor device and the like and corresponding power distribution devices need to be connected by adopting the cable, but the current of the cable is mainly concentrated on the outer surface of the cable in the process of transmitting the electric energy, so that the cable generates more heat, the cable is burnt, and a fire disaster is caused and spread.
Originally, in order to improve the flame retardance of cables, halogen-containing flame retardants are generally added, however, during the combustion process of the cables, a large amount of smoke and hydrogen halide gas are released, people are suffocated in fire disasters, meanwhile, the cables are highly corrosive to instruments and equipment, and so-called secondary disasters are caused, so that the development and the use of low-smoke, low-halogen and halogen-free flame retardant materials are one of the development directions of cables and other fields.
At present, most of the conventional halogen-free low-smoke flame-retardant materials are prepared by adding hydroxide (such as aluminum hydroxide and the like) into a polyolefin substrate as a flame-retardant system, so that a certain flame-retardant effect can be achieved, but the dosage is large, the flame-retardant efficiency is low, the flame-retardant efficiency can only meet the common flame-retardant requirement, in addition, the hydroxide particles are easy to agglomerate and can not be stably and uniformly dispersed in the material system, so that the negative influence is generated on the flame-retardant property of the final material, and the mechanical property of the final material is reduced, such as the reduction of tensile strength and elongation at break.
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 novel capsule flame retardant and having high flame retardant property, flame retardant durability, good combustion smoke suppression effect and good processing formability 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 novel capsule flame retardant is prepared from the following raw materials in parts by weight: 40-60 parts of ethylene-vinyl acetate copolymer, 20-40 parts of fluorosilicone rubber, 10-20 parts of terpene resin, 20-30 parts of metallocene polyethylene, 25-40 parts of capsule flame retardant, 15-25 parts of compatilizer, 5-10 parts of reinforcing agent, 3-9 parts of stabilizer, 0.3-0.8 part of peroxide cross-linking agent, 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).
In one embodiment, the fluorosilicone rubber has a decrease in tensile strength at 225 ℃ for 72 hours of not more than 35% from its initial tensile strength and a decrease in elongation at break of not more than 30% from its initial elongation at break.
Preferably, the fluorosilicone rubber can be selected from one or more of FSR8430-U, FSR8440-U, FSR8460-U or FSR8470-U which are sold in the market.
In one embodiment, the softening point of the terpene resin is 100-130 ℃, and the acid value of the terpene resin is 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.
As an embodiment, the metallocene polyethylene has a melt index of 3 to 5g/10min (190 ℃, 2.16 kg).
As an embodiment, the capsule flame retardant is prepared as follows:
step i): under the condition of ice water bath, adding titanium tetrachloride into deionized water to prepare titanium tetrachloride solution, then heating the titanium tetrachloride solution to 60-70 ℃, dropwise adding ammonia water with the concentration of 20-25 wt% at a constant speed while stirring, carrying out hydrolysis reaction for 1-2 h, stopping adding the ammonia water when the pH value of the solution is 7.5-8, and carrying out ultrasonic treatment to obtain an intermediate suspension;
step ii): adding ammonium polyphosphate and expandable graphite into absolute ethyl alcohol at normal temperature, and performing ultrasonic treatment to obtain a dispersion liquid;
step iii): and (3) adding the dispersion liquid prepared in the step ii) into the intermediate suspension liquid prepared in the step i), then dropwise adding a 10-15 wt% sodium hydroxide aqueous solution at a constant speed under stirring in a water bath condition at 75-90 ℃, reacting for 1-2 h under stirring, stopping adding the sodium hydroxide aqueous solution, keeping the temperature for 15-30 min, and then carrying out suction filtration, washing, drying and grinding to obtain the capsule flame retardant.
Preferably, the volume ratio of the titanium tetrachloride to the deionized water in the step i) is 1-2:10, and the dropping speed of the ammonia water is 5-10 mu L/s; in the step ii), the mass ratio of the ammonium polyphosphate to the expandable graphite is 10:1-3, and the mass ratio of the ammonium polyphosphate to the absolute ethyl alcohol is 1: 10-50; the volume ratio of the dispersion liquid to the intermediate suspension liquid is 1: 1-3.
Preferably, the dropping speed of the sodium hydroxide aqueous solution in the step iii) is 0.5-3 μ L/s, the drying temperature is 100-110 ℃, and the drying time is 6-12 h.
In one embodiment, the compatibilizer is maleic anhydride grafted EVA.
Preferably, the grafting ratio of the maleic anhydride grafted EVA is 1.2-1.8%, and the melt index is 2-5 g/10min (190 ℃, 2.16 kg).
As an embodiment, the reinforcing agent is fumed silica.
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).
In one embodiment, the peroxide crosslinking agent is one or more of bis (4-methylbenzoyl) peroxide, tert-butyl peroxy-2-ethylhexyl carbonate or 1, 1-bis (tert-butyl peroxy) cyclohexane.
As an embodiment, the lubricant is selected from at least one of natural paraffin, liquid paraffin, microcrystalline paraffin, polyethylene wax, butyl stearate, oleamide, ethylene bis stearamide, silicone powder.
In one embodiment, the antioxidant is selected from at least one of 2, 6-di-tert-butyl-p-cresol, octadecyl beta (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3 tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 2 ' -methylenebis (4-ethyl-6-tert-butylphenol), 1,3, 5-tris (3, 5-tert-butyl-4-hydroxybenzyl) trimethylbenzene, 2 ' -methylenebis (4-methyl-6-tert-butylphenol), 4 ' -di-tert-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 novel encapsulated flame retardant, the method comprising the following steps:
step 1): uniformly stirring and mixing ethylene-vinyl acetate copolymer, metallocene polyethylene, compatilizer, capsule flame retardant, stabilizer, peroxide crosslinking agent, lubricant and 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, and cooling, drying and granulating after extrusion to obtain the low-smoke halogen-free cable material.
As a preferred technical scheme, the temperature of the first zone of the double-screw extruder is 210-.
Compared with the prior art, the invention has the following characteristics:
1) the cable material of the invention takes ethylene-vinyl acetate copolymer and metallocene polyethylene as main base materials, introduces fluorosilicone rubber to enhance the toughness and weather aging resistance of the base materials, is favorable for improving the medium resistance of the base materials because the fluorosilicone rubber carries fluorine-containing groups, can improve the tolerance of a material system to organic solvents, oil substances and acid and alkali substances, has the same silica skeleton as a reinforcing agent aiming at the fluorosilicone rubber, and can stably fill the gaps of the internal cross-linked network of the fluorosilicone rubber so as to form stronger interaction, not only can enhance the strength of the fluorosilicone rubber, but also can disperse in the ethylene-vinyl acetate copolymer and the metallocene polyethylene base materials by taking the fluorosilicone rubber as a carrier, the heat resistance and the electric resistance of the base material can be effectively improved, so that the final material has excellent electric insulation and flame retardance, and the terpene resin and the fluorosilicone rubber are compounded, so that the adhesion between the fluorosilicone rubber particles and the base material is enhanced, the fluorosilicone rubber can be stably fused in the base material, and the aging resistance of the base material can be further improved;
2) in order to improve the flame retardant property of the cable material, the invention adopts the capsule flame retardant, which is prepared by coating ammonium polyphosphate doped with expandable graphite on the surface of organically synthesized titanium dioxide particles, the flame retardancy of the ammonium polyphosphate and the expandable graphite can be organically combined with the smoke suppression property of the titanium dioxide, the ammonium polyphosphate and the expandable graphite can play a role of flame retardance and synergy together, the flame retardant effect is optimized, when the cable material is burnt and heated, the ammonium polyphosphate on the outer layer and the expandable graphite are combined with each other to form a compact and stable expanded carbon layer, the titanium dioxide particles in the cable material can be released and filled in the formed expanded carbon layer, so that the diffusion channel of combustible gas and oxygen is blocked, the heat release rate of the material can be obviously reduced, the generation and the diffusion of smoke can be effectively inhibited, in addition, the average particle size of the capsule flame retardant is about 1.2-1.5 mu m, the flame retardant has excellent dispersibility in base resin, so that the material system is endowed with excellent flame retardant and smoke suppression effects;
3) the cable material disclosed by the invention is simple in preparation process, good in molding processability, oil stain resistance, good in weather resistance, excellent in flame retardant and smoke suppression effects, good in mechanical strength and toughness, capable of ensuring the working performance and the service life of the cable, greatly improving the safety and the reliability of the cable in use and good in application prospect.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to specific embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and 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 cable material of the embodiment is prepared from the following raw materials in parts by weight: 40 parts of ethylene-vinyl acetate copolymer, 20 parts of fluorosilicone rubber, 10 parts of terpene resin, 20 parts of metallocene polyethylene, 25 parts of capsule flame retardant, 15 parts of compatilizer, 5 parts of reinforcing agent, 3 parts of stabilizer, 0.3 part of peroxide crosslinking agent, 0.5 part of lubricant and 0.2 part of antioxidant.
Wherein the ethylene-vinyl acetate copolymer has a vinyl acetate content of 12wt% 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 TP 1105; the metallocene polyethylene used had a melt index of 3g/10min (190 ℃, 2.16 kg); the compatibilizer used was maleic anhydride grafted EVA with a grafting yield of 1.2% and a melt index of about 2 g/10min (190 ℃, 2.16 kg); the reinforcing agent is fumed silica; the stabilizer is dibutyltin maleate; the peroxide crosslinking agent is di (4-methylbenzoyl) peroxide, and the lubricant is polyethylene wax; the antioxidant used was 2, 6-di-tert-butyl-p-cresol.
The preparation method of the capsule flame retardant used in the example is as follows:
step i): under the condition of ice water bath, adding titanium tetrachloride into deionized water to prepare titanium tetrachloride solution, then heating the titanium tetrachloride solution to about 60 ℃, dropwise adding ammonia water with the concentration of about 20 wt% at a constant speed while stirring, carrying out hydrolysis reaction for about 2 hours, wherein the pH value of the solution is about 7.5, stopping adding the ammonia water, and carrying out ultrasonic treatment to prepare an intermediate suspension;
step ii): adding ammonium polyphosphate and expandable graphite into absolute ethyl alcohol at normal temperature, and performing ultrasonic treatment to obtain a dispersion liquid;
step iii): and (3) adding the dispersion liquid prepared in the step ii) into the intermediate suspension liquid prepared in the step i), then dropwise adding a sodium hydroxide aqueous solution with the concentration of about 10 wt% at a constant speed under the condition of a water bath at about 75 ℃, stirring and reacting for about 2 hours, stopping adding the sodium hydroxide aqueous solution, keeping the temperature for about 30 minutes, and then carrying out suction filtration, washing, drying and grinding to obtain the capsule flame retardant.
In the preparation method, the volume ratio of the titanium tetrachloride to the deionized water in the step i) is about 1:10, and the dropping speed of the ammonia water is about 5 mu L/s; the mass ratio of the ammonium polyphosphate to the expandable graphite in the step ii) is about 10:1, and the mass ratio of the ammonium polyphosphate to the absolute ethyl alcohol is about 1: 10; the volume ratio of the dispersion to the intermediate suspension is about 1: 1; the dropping speed of the aqueous solution of sodium hydroxide in step iii) was about 0.5. mu.L/s, the drying temperature was about 100 ℃ and the drying time was about 12 hours.
Example 2:
the cable material of the embodiment 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 metallocene polyethylene, 40 parts of capsule flame retardant, 25 parts of compatilizer, 10 parts of reinforcing agent, 9 parts of stabilizer, 0.8 part of peroxide crosslinking agent, 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 TP 1115; the metallocene polyethylene used had a melt index of 5g/10min (190 ℃, 2.16 kg); the compatibilizer used was maleic anhydride grafted EVA with a grafting yield of 1.8% and a melt index of about 5g/10min (190 ℃, 2.16 kg); the reinforcing agent is fumed silica; the stabilizer used is dibutyltin dilaurate; the peroxide crosslinking agent used is 1, 1-di (tert-butylperoxy) cyclohexane; the lubricant used was butyl stearate; the antioxidant used was octadecyl beta (3,5 di-tert-butyl-4-hydroxyphenyl) propionate.
The preparation method of the capsule flame retardant used in the example is as follows:
step i): under the condition of ice water bath, adding titanium tetrachloride into deionized water to prepare titanium tetrachloride solution, then heating the titanium tetrachloride solution to about 70 ℃, dropwise adding ammonia water with the concentration of about 25wt% at a constant speed while stirring, carrying out hydrolysis reaction for about 1 h, wherein the pH value of the solution is about 8, stopping adding the ammonia water, and carrying out ultrasonic treatment to prepare intermediate suspension;
step ii): adding ammonium polyphosphate and expandable graphite into absolute ethyl alcohol at normal temperature, and performing ultrasonic treatment to obtain a dispersion liquid;
step iii): and (3) adding the dispersion liquid prepared in the step ii) into the intermediate suspension liquid prepared in the step i), then dropwise adding a sodium hydroxide aqueous solution with the concentration of about 15wt% at a constant speed under the condition of a water bath at about 90 ℃, stirring and reacting for about 1 h, stopping adding the sodium hydroxide aqueous solution, keeping the temperature for about 15 min, and then carrying out suction filtration, washing, drying and grinding to obtain the capsule flame retardant.
In the preparation method, the volume ratio of the titanium tetrachloride to the deionized water in the step i) is about 2:10, and the dropping speed of the ammonia water is about 10 mu L/s; the mass ratio of ammonium polyphosphate to expandable graphite in step ii) is about 10:3, and the mass ratio of ammonium polyphosphate to absolute ethyl alcohol is about 1: 50; the volume ratio of the dispersion to the intermediate suspension is about 1: 3; the dropping speed of the aqueous solution of sodium hydroxide in step iii) was about 3. mu.L/s, the drying temperature was about 110 ℃ and the drying time was about 6 hours.
Example 3:
the cable material of the embodiment is prepared from the following raw materials in parts by weight: 52 parts of ethylene-vinyl acetate copolymer, 28 parts of fluorosilicone rubber, 15 parts of terpene resin, 20 parts of metallocene polyethylene, 35 parts of capsule flame retardant, 20 parts of compatilizer, 8 parts of reinforcing agent, 6 parts of stabilizer, 0.5 part of peroxide crosslinking agent, 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 TP 1125; the metallocene polyethylene used had a melt index of 4g/10min (190 ℃, 2.16 kg); the compatibilizer used was maleic anhydride grafted EVA with a grafting ratio of 1.4% and a melt index of about 3g/10min (190 ℃, 2.16 kg); the reinforcing agent is fumed silica; the stabilizer is prepared by mixing dibutyltin laurate maleate and di-n-octyltin maleate according to the mass ratio of 1: 1; the lubricant is prepared by mixing natural paraffin, polyethylene wax and ethylene bis stearamide according to the mass ratio of 1:1: 3; the peroxide crosslinking agent is tert-butyl peroxy-2-ethylhexyl carbonate; the antioxidant is prepared by mixing 1,1, 3-tri (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 2' -methylene bis (4-ethyl-6-tert-butylphenol) and 1,3, 5-tri (3, 5-tert-butyl-4-hydroxybenzyl) trimethylbenzene in a mass ratio of 5:2: 3.
The preparation method of the capsule flame retardant used in the example is as follows:
step i): under the condition of ice water bath, adding titanium tetrachloride into deionized water to prepare a titanium tetrachloride solution, then heating the titanium tetrachloride solution to about 65 ℃, dropwise adding ammonia water with the concentration of about 24 wt% while stirring at a constant speed, carrying out hydrolysis reaction for about 1.6 h, stopping adding the ammonia water when the pH value of the solution is about 7.8, and carrying out ultrasonic treatment to obtain an intermediate suspension;
step ii): adding ammonium polyphosphate and expandable graphite into absolute ethyl alcohol at normal temperature, and performing ultrasonic treatment to obtain a dispersion liquid;
step iii): and (3) adding the dispersion liquid prepared in the step ii) into the intermediate suspension liquid prepared in the step i), then dropwise adding a sodium hydroxide aqueous solution with the concentration of about 12wt% at a constant speed under the condition of a water bath at about 82 ℃, stirring and reacting for about 1.2 h, stopping adding the sodium hydroxide aqueous solution, keeping the temperature for about 20 min, and then carrying out suction filtration, washing, drying and grinding to obtain the capsule flame retardant.
In the preparation method, the volume ratio of the titanium tetrachloride to the deionized water in the step i) is about 1.5:10, and the dropping speed of the ammonia water is about 6 mu L/s; the mass ratio of ammonium polyphosphate to expandable graphite in step ii) is about 10:2, and the mass ratio of ammonium polyphosphate to absolute ethyl alcohol is about 1: 40; the volume ratio of the dispersion to the intermediate suspension is about 1: 2; the dropping speed of the aqueous solution of sodium hydroxide in step iii) was about 1. mu.L/s, the drying temperature was about 105 ℃ and the drying time was about 10 hours.
Example 4:
the cable material of the embodiment is prepared from the following raw materials in parts by weight: 45 parts of ethylene-vinyl acetate copolymer, 23 parts of fluorosilicone rubber, 12 parts of terpene resin, 26 parts of metallocene polyethylene, 32 parts of capsule flame retardant, 22 parts of compatilizer, 7 parts of reinforcing agent, 8 parts of stabilizer, 0.6 part of peroxide crosslinking agent, 0.8 part of lubricant and 0.6 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 TP 1125; the metallocene polyethylene used had a melt index of 5g/10min (190 ℃, 2.16 kg); the compatibilizer used was maleic anhydride grafted EVA with a grafting ratio of 1.4% and a melt index of about 3g/10min (190 ℃, 2.16 kg); the reinforcing agent is fumed silica; the stabilizer used is di-n-octyl tin bis (isooctyl thioglycolate); the peroxide crosslinking agent is formed by mixing bis (4-methylbenzoyl) peroxide and tert-butyl peroxy-2-ethylhexyl carbonate according to the mass ratio of 1: 3; the lubricant is formed by mixing microcrystalline paraffin, oleamide and silicone powder according to the mass ratio of 1:1: 1; the antioxidant used was 2, 2' -methylenebis (4-methyl-6-tert-butylphenol).
The preparation method of the capsule flame retardant used in the example is as follows:
step i): under the condition of ice water bath, adding titanium tetrachloride into deionized water to prepare titanium tetrachloride solution, then heating the titanium tetrachloride solution to about 68 ℃, dropwise adding ammonia water with the concentration of about 22 wt% while stirring at a constant speed, carrying out hydrolysis reaction for about 1.8 h, stopping adding the ammonia water when the pH value of the solution is about 7.6, and carrying out ultrasonic treatment to obtain an intermediate suspension;
step ii): adding ammonium polyphosphate and expandable graphite into absolute ethyl alcohol at normal temperature, and performing ultrasonic treatment to obtain a dispersion liquid;
step iii): and (3) adding the dispersion liquid prepared in the step ii) into the intermediate suspension liquid prepared in the step i), then dropwise adding a sodium hydroxide aqueous solution with the concentration of about 15wt% at a constant speed under the condition of a water bath at about 80 ℃, stirring and reacting for about 1.5 h, stopping adding the sodium hydroxide aqueous solution, keeping the temperature for about 25 min, and then carrying out suction filtration, washing, drying and grinding to obtain the capsule flame retardant.
In the preparation method, the volume ratio of the titanium tetrachloride to the deionized water in the step i) is about 1.8:10, and the dropping speed of the ammonia water is about 8 mu L/s; the mass ratio of ammonium polyphosphate to expandable graphite in step ii) is about 10:2, and the mass ratio of ammonium polyphosphate to absolute ethyl alcohol is about 1: 30; the volume ratio of the dispersion to the intermediate suspension is about 1: 3; the dropping speed of the aqueous solution of sodium hydroxide in step iii) was about 1.5. mu.L/s, the drying temperature was about 105 ℃ and the drying time was about 10 hours.
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, metallocene polyethylene, compatilizer, capsule flame retardant, stabilizer, peroxide crosslinking agent, lubricant and 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 218 ℃, the temperature of the second zone is 225 ℃, the temperature of the third zone is 235 ℃, the temperature of the fourth zone is 240 ℃, the temperature of the fifth zone is 245 ℃, the temperature of the sixth zone is 250 ℃, the temperature of the seventh zone is 250 ℃, the temperature of the eighth zone is 235 ℃ and the temperature of the ninth zone is 220 ℃.
Comparative example 1:
the comparative example cable material used ammonium polyphosphate as a flame retardant, the remainder being the same as example 3.
Comparative example 2:
the comparative example cable material used expandable graphite as a flame retardant was the same as example 3.
Comparative example 3:
this comparative example does not contain fluorosilicone rubber, terpene resin, and reinforcing agent, as in example 3.
The results of the performance tests of the cable materials prepared in examples 1 to 4 and comparative examples 1 to 3 are shown in table 1 below.
TABLE 1 test results
Note: the tensile strength and elongation at break tests in Table 1 were carried out in accordance with GB/T1040.3 and the impact strength was carried out in accordance with GB/T1043.
As can be seen from the test results in Table 1, the cable materials prepared in the embodiments 1 to 4 of the present invention have both excellent tensile strength and impact strength, are excellent in flame retardancy and insulation property, and have 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, portions of different embodiments, and various features recited 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 (10)
1. The low-smoke halogen-free cable material containing the novel capsule flame retardant is characterized by being prepared from the following raw materials in parts by weight: 40-60 parts of ethylene-vinyl acetate copolymer, 20-40 parts of fluorosilicone rubber, 10-20 parts of terpene resin, 20-30 parts of metallocene polyethylene, 25-40 parts of capsule flame retardant, 15-25 parts of compatilizer, 5-10 parts of reinforcing agent, 3-9 parts of stabilizer, 0.3-0.8 part of peroxide cross-linking agent, 0.5-1 part of lubricant and 0.2-1 part of antioxidant.
2. The low smoke zero halogen cable material containing the novel capsule flame retardant as claimed in 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 halogen-free cable material containing the novel encapsulated flame retardant as claimed in claim 1, wherein the fluorosilicone rubber has a tensile strength at 225 ℃ which is not more than 35% less than its initial tensile strength after 72 hours, and has an elongation at break which is not more than 30% less than its initial elongation at break.
4. The low-smoke zero-halogen cable material containing the novel encapsulated flame retardant as claimed in claim 1, wherein the softening point of the terpene resin is 100-130 ℃, and the acid value is less than 1.0 mg KOH/g.
5. The low smoke zero halogen cable material containing the novel encapsulated flame retardant as claimed in claim 1, wherein the metallocene polyethylene has a melt index of 3-5 g/10min (190 ℃, 2.16 kg).
6. The low-smoke halogen-free cable material containing the novel capsule flame retardant is characterized in that the preparation method of the capsule flame retardant is as follows:
step i): under the condition of ice water bath, adding titanium tetrachloride into deionized water to prepare titanium tetrachloride solution, then heating the titanium tetrachloride solution to 60-70 ℃, dropwise adding ammonia water with the concentration of 20-25 wt% at a constant speed while stirring, carrying out hydrolysis reaction for 1-2 h, keeping the pH value of the solution at 7.5-8, stopping adding the ammonia water, continuing the reaction for 30-60 min, and then carrying out ultrasound treatment to obtain an intermediate suspension;
step ii): adding ammonium polyphosphate and expandable graphite into absolute ethyl alcohol at normal temperature, and then carrying out ultrasonic treatment to obtain a dispersion liquid;
step iii): and (3) adding the dispersion liquid prepared in the step ii) into the intermediate suspension liquid prepared in the step i), then dropwise adding a 10-15 wt% sodium hydroxide aqueous solution at a constant speed under stirring in a water bath condition at 75-90 ℃, reacting for 1-2 h under stirring, stopping adding the sodium hydroxide aqueous solution, keeping the temperature for 15-30 min, and then carrying out suction filtration, washing, drying and grinding to obtain the capsule flame retardant.
7. The low-smoke halogen-free cable material containing the novel capsule flame retardant as claimed in claim 6, wherein the volume ratio of the titanium tetrachloride to the deionized water in step i) is 1-2:10, and the dropping speed of the ammonia water is 5-10 μ L/s; in the step ii), the mass ratio of the ammonium polyphosphate to the expandable graphite is 10:1-3, and the mass ratio of the ammonium polyphosphate to the absolute ethyl alcohol is 1: 10-50; the volume ratio of the dispersion liquid to the intermediate suspension liquid is 1: 1-3.
8. The low-smoke halogen-free cable material containing the novel encapsulated flame retardant as claimed in claim 6, wherein the dropping speed of the sodium hydroxide aqueous solution in step iii) is 0.5-3 μ L/s, the drying temperature is 100-110 ℃, and the drying time is 6-12 h.
9. The low smoke zero halogen cable material containing the novel capsule flame retardant as claimed in claim 1, wherein the compatibilizer is maleic anhydride grafted EVA, the reinforcing agent is fumed silica, the stabilizer is an organotin heat stabilizer, the peroxide crosslinking agent is one or more of bis (4-methylbenzoyl) peroxide, tert-butylperoxy-2-ethylhexyl carbonate or 1, 1-bis (tert-butylperoxy) cyclohexane, the lubricant is at least one selected from natural paraffin, liquid paraffin, microcrystalline paraffin, polyethylene wax, butyl stearate, oleamide, ethylene bis stearamide and silicone powder, and the antioxidant is at least one selected from 2, 6-di-tert-butyl-p-cresol, beta (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate, 1,1,3 tris (2-methyl-4 hydroxy-5-tert-butylphenyl) butane, 2 ' -methylenebis (4-ethyl-6-tert-butylphenol), 1,3, 5-tris (3, 5-tert-butyl-4-hydroxybenzyl) trimethylbenzene, 2 ' -methylenebis (4-methyl-6-tert-butylphenol), and 4,4 ' -di-tert-octyldiphenylamine.
10. The preparation method of the low-smoke halogen-free cable material containing the novel encapsulated flame retardant as claimed in any one of claims 1 to 9, wherein the method comprises the following steps:
step 1): uniformly stirring and mixing ethylene-vinyl acetate copolymer, metallocene polyethylene, compatilizer, capsule flame retardant, stabilizer, peroxide crosslinking agent, lubricant and 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, and cooling, drying and granulating after extrusion to obtain the low-smoke halogen-free cable material.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113831630A (en) * | 2021-09-28 | 2021-12-24 | 福建通宇电缆有限公司 | Flame-retardant cable and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101503526A (en) * | 2009-03-05 | 2009-08-12 | 中国科学技术大学 | Aqueous polyurethane micro-encapsulated halogen-free flame retardant and preparation thereof |
| CN103073862A (en) * | 2013-01-10 | 2013-05-01 | 苏州安鸿泰新材料有限公司 | Halogen-free flame-retardant polylactic acid nanocomposite and preparation method thereof |
| CN103205099A (en) * | 2012-12-14 | 2013-07-17 | 青岛博益特生物材料有限公司 | Microencapsulated flame retardant alloy making method |
| CN106496757A (en) * | 2016-11-07 | 2017-03-15 | 中广核三角洲（中山）高聚物有限公司 | A kind of resistance to 150 DEG C are exempted from irradiation oil-resistant low-smoke halogen-free flame-retardant cable material of polyolefin and preparation method thereof |
| WO2017070893A1 (en) * | 2015-10-29 | 2017-05-04 | 国家纳米科学中心 | Ceramic silicone rubber, preparation method and use thereof |
| CN109181004A (en) * | 2018-09-28 | 2019-01-11 | 黄旭东 | A kind of preparation method of microcapsule flame retardant |
-
2021
- 2021-02-02 CN CN202110139296.5A patent/CN112795079B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101503526A (en) * | 2009-03-05 | 2009-08-12 | 中国科学技术大学 | Aqueous polyurethane micro-encapsulated halogen-free flame retardant and preparation thereof |
| CN103205099A (en) * | 2012-12-14 | 2013-07-17 | 青岛博益特生物材料有限公司 | Microencapsulated flame retardant alloy making method |
| CN103073862A (en) * | 2013-01-10 | 2013-05-01 | 苏州安鸿泰新材料有限公司 | Halogen-free flame-retardant polylactic acid nanocomposite and preparation method thereof |
| WO2017070893A1 (en) * | 2015-10-29 | 2017-05-04 | 国家纳米科学中心 | Ceramic silicone rubber, preparation method and use thereof |
| CN106496757A (en) * | 2016-11-07 | 2017-03-15 | 中广核三角洲（中山）高聚物有限公司 | A kind of resistance to 150 DEG C are exempted from irradiation oil-resistant low-smoke halogen-free flame-retardant cable material of polyolefin and preparation method thereof |
| CN109181004A (en) * | 2018-09-28 | 2019-01-11 | 黄旭东 | A kind of preparation method of microcapsule flame retardant |
Non-Patent Citations (1)
| Title |
|---|
| 吴灿: "聚磷酸铵（APP）微胶囊化及其应用", 《中国优秀博硕士学位论文全文数据库（硕士） 工程科技I辑》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113831630A (en) * | 2021-09-28 | 2021-12-24 | 福建通宇电缆有限公司 | Flame-retardant cable and preparation method thereof |
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