CN112795079B - Low-smoke halogen-free cable material containing novel capsule flame retardant and preparation thereof - Google Patents
Low-smoke halogen-free cable material containing novel capsule flame retardant and preparation 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
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
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- 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
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
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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
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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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
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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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
- 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
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 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.
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 under the condition of a water bath at 75-90 ℃, dropwise adding a 10-15 wt% sodium hydroxide aqueous solution at a constant speed while stirring, stirring for reacting for 1-2 h, stopping adding the sodium hydroxide aqueous solution, keeping the temperature for 15-30 min, and then performing 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; in the step ii), the mass ratio of the ammonium polyphosphate to the expandable graphite is (10) - (3), and the mass ratio of the ammonium polyphosphate to the anhydrous ethanol is (1); the volume ratio of the dispersion liquid to the intermediate suspension liquid is 1.
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.
As an 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).
As an 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.
As an 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;
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 preferable 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 and the metallocene polyethylene as main base materials, the fluorosilicone rubber is introduced to enhance the toughness and weather aging resistance of the base materials, the fluorosilicone rubber carries a fluorine-containing group, so that the medium resistance of the base materials can be 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 is-Si-O-, the fumed silica is taken as a reinforcing agent as an auxiliary, the molecular main chain structural unit and the fumed silica have the same silica framework, and the fumed silica 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 used as a carrier and is dispersed in the ethylene-vinyl acetate copolymer and the metallocene polyethylene base materials, the heat resistance and the electrical resistance of the base materials can be effectively improved, so that the final material has excellent electrical insulation and flame retardance, and the terpene resin and the fluorosilicone rubber phase are favorable for enhancing the adhesion between fluorosilicone rubber particles and can be stably fused in the base materials, and further improve the aging resistance of the base materials;
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, so that 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 emission 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, and the capsule flame retardant has excellent dispersibility in base material resin, thereby endowing the material system with excellent flame retardance 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 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 detailed embodiments and specific operation procedures 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 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 cross-linking 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 TP1105; 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; the mass ratio of ammonium polyphosphate to expandable graphite in step ii) is about 10, and the mass ratio of ammonium polyphosphate to anhydrous ethanol is about 1; the volume ratio of dispersion to intermediate suspension is about 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 TP1115; 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 1.8% 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 (t-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 hour, enabling the pH value of the solution to be about 8, 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 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; the mass ratio of ammonium polyphosphate to expandable graphite in step ii) is about 10, and the mass ratio of ammonium polyphosphate to anhydrous ethanol is about 1; the volume ratio of dispersion to intermediate suspension is about 1; 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 sold in the market; the terpene resin used was commercially available TP1125; 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; the lubricant is prepared by mixing natural paraffin, polyethylene wax and ethylene bis stearamide according to a mass ratio of 1; the peroxide crosslinking agent is tert-butyl peroxy-2-ethylhexyl carbonate; the antioxidant is prepared by mixing 1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 2' -methylene bis (4-ethyl-6-tert-butylphenol) and 1,3, 5-tris (3, 5-tert-butyl-4-hydroxybenzyl) trimethylbenzene in a mass ratio of 5.
The preparation method of the capsule flame retardant used in this 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 under the condition of a water bath at about 82 ℃, dropwise adding a sodium hydroxide aqueous solution with the concentration of about 12wt% at a constant speed while stirring, stirring for 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; the mass ratio of ammonium polyphosphate to expandable graphite in step ii) is about 10; the volume ratio of dispersion to intermediate suspension is about 1; 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 TP1125; 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 (isooctyl thioglycolate) di-n-octyl tin; the peroxide crosslinking agent is formed by mixing bis (4-methylbenzoyl) peroxide and tert-butyl peroxy-2-ethylhexyl carbonate according to a mass ratio of 1; the lubricant is prepared by mixing microcrystalline paraffin, oleamide and silicone powder according to the mass ratio of 1; the antioxidant used was 2,2' -methylenebis (4-methyl-6-tert-butylphenol).
The preparation method of the capsule flame retardant used in this 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 under the condition of a water bath at the temperature of about 80 ℃, dropwise adding a sodium hydroxide aqueous solution with the concentration of about 15wt% at a constant speed while stirring, stirring for 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; the mass ratio of ammonium polyphosphate to expandable graphite in step ii) is about 10, and the mass ratio of ammonium polyphosphate to anhydrous ethanol is about 1; the volume ratio of dispersion to intermediate suspension is about 1; 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 examples 1-4 above 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, the temperature of the second zone, the temperature of the third zone, the temperature of the fourth zone, the temperature of the fifth zone, the temperature of the sixth zone, the temperature of the seventh zone, the temperature of the eighth zone and the temperature of the ninth zone of the double-screw extruder are 218 ℃, 225 ℃, 240 ℃ and 250 ℃ respectively.
Comparative example 1:
the comparative example cable material uses ammonium polyphosphate as a flame retardant, and the rest is 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 (9)
1. A low-smoke halogen-free cable material containing a 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;
the preparation method of the capsule flame retardant comprises the following steps:
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.
2. The low smoke zero halogen cable material containing the novel encapsulated 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, characterized in that 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 as claimed in claim 1, wherein the volume ratio of the titanium tetrachloride to the deionized water in step i) is 1-2; in the step ii), the mass ratio of the ammonium polyphosphate to the expandable graphite is 10-3, and the mass ratio of the ammonium polyphosphate to the absolute ethyl alcohol is 1; the volume ratio of the dispersion to the intermediate suspension is 1.
7. The low-smoke halogen-free cable material containing the novel encapsulated flame retardant as claimed in claim 1, 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.
8. The low smoke zero halogen cable material containing the novel capsule flame retardant of 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, t-butylperoxy-2-ethylhexyl carbonate or 1, 1-bis (t-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-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' -methylene bis (4-di-t-octylphenol) and 4' -di-t-butyl-octylphenol.
9. The preparation method of the low smoke zero halogen cable material containing the novel encapsulated flame retardant according to any one of claims 1 to 8, characterized by 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.
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| 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 |
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