CN114350052A - Polyethylene cable material with fireproof and flame-retardant functions - Google Patents
Polyethylene cable material with fireproof and flame-retardant functions Download PDFInfo
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Abstract
The invention discloses a polyethylene cable material with fireproof and flame-retardant functions, which is prepared from the following raw materials in parts by weight: 35-45 parts of polyethylene or aging-resistant polyethylene master batch, 15-25 parts of PBT resin, 10-20 parts of ethylene-methyl acrylate copolymer, 5-15 parts of maleic anhydride grafted ethylene-octene copolymer, 1-2 parts of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate, 3-8 parts of coumarone resin, 2-4 parts of zinc stearate, 1-10 parts of trimethylolpropane triacrylate, 1-5 parts of didecyl phthalate, and 5-15 parts of zirconium phosphate or functionalized zirconium phosphate. The polyethylene cable material with the fireproof and flame-retardant functions, which is prepared by the invention, has the advantages of good fireproof and flame-retardant effects, excellent mechanical strength and aging resistance, long service life, environmental protection and no pollution.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a polyethylene cable material with fireproof and flame-retardant functions.
Background
The cable material is used for the insulation and the sheath of the electric wire and the cable, and comprises different types of rubber, plastic, nylon and the like. The polyolefin resin has good mechanical property, insulating property, low temperature resistance and processability, and is one of the commonly used raw materials of the cable material. When in use, the aging and the damage of the cable material are easy to cause fire, and if the cable material is burnt, a large amount of smoke and toxic gas can be released, so that the safe evacuation and the fire extinguishing and rescue can be seriously influenced. Therefore, it is very important to improve the aging resistance, flame retardance, strength and other properties of the cable material.
Chinese patent CN104231466A discloses a graft cross-linked polyethylene cable material, which comprises the following raw materials: polyvinyl chloride resin, PBT resin, magnesium oxide, aluminum hydroxide, stearic acid, silica gel and inorganic filler. The cable material of this patent can effectually protect the copper body to avoid the oxidation, and can not damage the copper body itself, has prolonged the life of cable material, has practiced thrift the cost, but the fire behavior and the tensile strength of cable material still need improve.
Disclosure of Invention
In view of the above-mentioned defects of the prior art, the present invention provides a polyethylene cable material with fireproof and flame-retardant functions.
A polyethylene cable material with fireproof and flame-retardant functions is composed of the following raw materials in parts by weight: 35-45 parts of polyethylene or aging-resistant polyethylene master batch, 15-25 parts of PBT resin, 10-20 parts of ethylene-methyl acrylate copolymer, 5-15 parts of maleic anhydride grafted ethylene-octene copolymer, 1-2 parts of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate, 3-8 parts of coumarone resin, 2-4 parts of zinc stearate, 1-10 parts of trimethylolpropane triacrylate, 1-5 parts of didecyl phthalate, and 5-15 parts of zirconium phosphate or functionalized zirconium phosphate.
Preferably, the polyethylene cable material with the fireproof and flame-retardant functions comprises the following raw materials in parts by weight: 35-45 parts of aging-resistant polyethylene master batch, 15-25 parts of PBT resin, 10-20 parts of ethylene-methyl acrylate copolymer, 5-15 parts of maleic anhydride grafted ethylene-octene copolymer, 1-2 parts of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate, 3-8 parts of coumarone resin, 2-4 parts of zinc stearate, 1-10 parts of trimethylolpropane triacrylate, 1-5 parts of didecyl phthalate and 5-15 parts of functionalized zirconium phosphate.
The preparation method of the aging-resistant polyethylene master batch comprises the following steps:
mixing methacryloxymethyltriethoxysilane, nano silicon dioxide, nano zirconium dioxide and 75-90 wt% of isopropanol aqueous solution according to the mass ratio of (3-5) to (20-25) to (5-10) to (30-50) at 40-60 ℃, carrying out ultrasonic treatment for 0.5-1h, wherein the ultrasonic frequency is 20-40kHz, the ultrasonic power is 300-500W, centrifuging, taking precipitate, and drying to obtain the pretreated inorganic filler; 70-80 parts of polyethylene, 3-5 parts of pretreatment inorganic filler, 3-5 parts of 4-acryloxy-2-hydroxybenzophenone, 1-3 parts of dilauryl thiodipropionate and 0.1-0.6 part of oleamide by weight are added into an internal mixer to be mixed and banned for 1-2 hours, and then the mixture is added into a double-screw extruder to be extruded and granulated, wherein the extrusion temperature is 110-130 ℃, and the anti-aging polyethylene master batch is obtained.
The preparation method of the functionalized zirconium phosphate comprises the following steps:
mixing zirconium phosphate and water according to the mass ratio of 1 (20-50) and carrying out ultrasonic treatment for 30-60min, wherein the ultrasonic frequency is 20-30kHz, the ultrasonic power is 500-; adding the pretreated zirconium phosphate into a ball mill, and ball-milling for 18-24h at the speed of 500-1500r/min to obtain zirconium phosphate powder; putting zirconium phosphate powder in a nitrogen atmosphere, heating to 400-600 ℃, and reacting for 3-7h to obtain layered zirconium phosphate; mixing the layered zirconium phosphate and Mg (NO)3)2·6H2O、Al(NO3)3·9H2Adding O into water for ultrasonic treatment for 10-30min, wherein the ultrasonic frequency is 20-30kHz, the ultrasonic power is 500-1000W, and the layered zirconium phosphate and Mg (NO) are added3)2·6H2O、Al(NO3)3·9H2The mass ratio of O to water is (2-4): (0.5-1): 1-2): 15-30, then heating to 70-90 ℃, simultaneously adjusting the pH to 9-10 by adopting 2-4mol/L sodium hydroxide aqueous solution, keeping 70-90 ℃ for reaction for 3-6h, centrifuging to obtain precipitate, and drying to obtain zirconium phosphate intercalation magnalium layered double hydroxide; adding zirconium phosphate intercalation magnalium layered double hydroxide and gamma-glycidyl ether oxypropyl trimethoxy silane into water, uniformly mixing, heating to 60-80 ℃ for reaction for 2-4h, then adding functional auxiliary agent, keeping 70-90 ℃ for reaction for 5-10h, centrifuging to obtain precipitate, and drying to obtain the functionalized zirconium phosphate, wherein the mass ratio of the zirconium phosphate intercalation magnalium layered double hydroxide, the gamma-glycidyl ether oxypropyl trimethoxy silane, the functional auxiliary agent and the water is (3-7): 1-3): 2-5): 10-20.
The functional auxiliary agent is one or a mixture of melamine cyanurate and ammonium polyphosphate; preferably, the functional assistant is a mixture of melamine cyanurate and ammonium polyphosphate in a mass ratio of (1-2) to (2-4).
The addition of the zirconium phosphate is beneficial to promoting the generation of carbon slag, the flame retardant property of the material is improved, and the zirconium phosphate has high adjustability and easy embeddability in the cable material. The inventor further researches to discover that the zirconium phosphate is treated to obtain the layered zirconium phosphate, and the layered zirconium phosphate and Mg (NO) are adopted3)2·6H2O、Al(NO3)3·9H2Preparing zirconium phosphate intercalation magnalium layered double hydroxide by O reaction, on one hand, preparing zirconium phosphate and magnalium layered double hydroxideThe combination can improve the flame retardant property of the cable material and has a synergistic effect, and the possible reasons are as follows: the zirconium phosphate has good surface carbonization and graphitization performance in the cable material, and the magnalium layered double hydroxide generates water in the combustion process and partially absorbs heat in the gasification process, so that the flame retardant effect is achieved; on the other hand, the zirconium phosphate and the magnesium-aluminum layered double hydroxide mutually improve the agglomeration problem of the zirconium phosphate and the magnesium-aluminum layered double hydroxide in the cable material, are beneficial to the compatibility and the dispersibility of the zirconium phosphate intercalation magnesium-aluminum layered double hydroxide in the cable material, and simultaneously improve the mechanical property of the cable material. The functional zirconium phosphate is prepared by grafting melamine cyanurate and ammonium polyphosphate on zirconium phosphate intercalation magnesium-aluminum layered double hydroxide through gamma-glycidyl ether oxypropyl trimethoxysilane, and organic matters in the functional zirconium phosphate are easy to have strong interaction with a cable material, so that the dispersion performance of the functional zirconium phosphate in the cable material is improved, and the mechanical property of the cable material is improved. The functional zirconium phosphate is carbonized at high temperature by melamine cyanurate in the combustion process, oxygen is blocked to improve the flame retardant property, ammonium polyphosphate can be decomposed into phosphoric acid in the combustion process and forms a carbon layer on the surface of a cable material, the melamine cyanurate and the ammonium polyphosphate act synergistically to obviously improve the flame retardant property of the cable material and simultaneously improve the mechanical property of the cable material.
The invention also discloses a preparation method of the polyethylene cable material with the fireproof and flame-retardant functions, which comprises the following steps: the method comprises the following steps: adding polyethylene or aging-resistant polyethylene master batch, PBT resin, ethylene-methyl acrylate copolymer, maleic anhydride grafted ethylene-octene copolymer, beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate, coumarone resin, zinc stearate, trimethylolpropane triacrylate, didecyl phthalate, zirconium phosphate or functionalized zirconium phosphate into an internal mixer, mixing and banburying for 20-30min, and then adding into a double-screw extruder for extrusion and granulation, wherein the temperature of the extrusion and granulation is 100-130 ℃, so as to obtain the polyethylene cable material with the fireproof and flame-retardant functions.
The invention has the beneficial effects that: the polyethylene cable material with the fireproof and flame-retardant functions, which is prepared by the invention, has the advantages of good fireproof and flame-retardant effects, excellent mechanical strength and aging resistance, long service life, environmental protection and no pollution. According to the invention, the functional zirconium phosphate is added into the raw material formula, melamine cyanurate is carbonized at high temperature during combustion, oxygen is blocked to improve the flame retardant property, ammonium polyphosphate is decomposed into phosphoric acid during combustion and forms a carbon layer on the surface of a cable material, the melamine cyanurate and the ammonium polyphosphate act synergistically to obviously improve the flame retardant property of the cable material, and meanwhile, the mechanical strength of the cable material is improved.
Detailed Description
Parameters, sources of specific chemicals in the examples:
polyethylene, high density polyethylene, type: h875017, melt index: 6-9 g/10min, particle size: 200 mesh, Shanghai Michelin Biochemical technology, Inc.
PBT resin, brand: 1401X07, brand: dendri PBT, injection grade, shanghai audio-plastic international trade ltd.
Ethylene-methyl acrylate copolymer, trade name: TC120, brand: DuPont, extrusion grade, Hangzhou Shengou plastication, Inc., USA.
Maleic anhydride grafted ethylene-octene copolymer, type: a2616, grafting ratio: 0.8-1%, Shanghai Kunjiao materials science and technology, Inc.
Octadecyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, CAS: 2082-79-3.
Coumarone resin, cat # s: 091 technical grade, Jinan Dahui chemical science and technology Limited.
Nanosilica, CAS: 7631-86-9, 30nm, Shanghai Ji to Biochemical technology, Inc.
Nano zirconium dioxide, CAS: 1314-23-4, 20nm, Zhejiang Yamei nanometer technology, Inc.
Methacryloxymethyltriethoxysilane, CAS: 5577-72-0.
Trimethylolpropane triacrylate, CAS: 15625-89-5,.
Didecyl phthalate, CAS: 84-77-5.
Zirconium phosphate, particle size: 1.7 μm, Mianzhu Yao Longgong chemical Co., Ltd.
Gamma-glycidoxypropyltrimethoxysilane, CAS: 2530-83-8.
Melamine cyanurate, CAS: 37640-57-6.
Ammonium polyphosphate, CAS: 68333-79-9, average degree of polymerization: 20MIN, Hubei Xin run chemical Co.
Example 1
A polyethylene cable material with fireproof and flame-retardant functions is composed of the following raw materials in parts by weight: 40 parts of polyethylene, 25 parts of PBT resin, 20 parts of ethylene-methyl acrylate copolymer, 15 parts of maleic anhydride grafted ethylene-octene copolymer, 2 parts of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate, 6 parts of coumarone resin, 3 parts of zinc stearate, 5 parts of trimethylolpropane triacrylate, 3 parts of didecyl phthalate and 10 parts of zirconium phosphate.
A preparation method of a polyethylene cable material with fireproof and flame-retardant functions comprises the following steps: adding polyethylene, PBT resin, ethylene-methyl acrylate copolymer, maleic anhydride grafted ethylene-octene copolymer, beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate, coumarone resin, zinc stearate, trimethylolpropane triacrylate, didecyl phthalate and zirconium phosphate into an internal mixer, mixing and banburying for 30min, adding into a double-screw extruder, and extruding and granulating at 120 ℃ to obtain the polyethylene cable material with the fireproof and flame-retardant functions.
Example 2
A polyethylene cable material with fireproof and flame-retardant functions is composed of the following raw materials in parts by weight: 40 parts of polyethylene, 25 parts of PBT resin, 20 parts of ethylene-methyl acrylate copolymer, 15 parts of maleic anhydride grafted ethylene-octene copolymer, 2 parts of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate, 6 parts of coumarone resin, 3 parts of zinc stearate, 5 parts of trimethylolpropane triacrylate, 3 parts of didecyl phthalate and 10 parts of functionalized zirconium phosphate.
The preparation method of the functionalized zirconium phosphate comprises the following steps: mixing zirconium phosphate and water according to a mass ratio of 1:30, carrying out ultrasonic treatment for 60min, wherein the ultrasonic frequency is 20kHz, the ultrasonic power is 500W, centrifuging, taking precipitate, and drying to obtain pretreated zirconium phosphate; adding the pretreated zirconium phosphate into a ball mill, and ball-milling for 20 hours at the speed of 600r/min to obtain zirconium phosphate powder; putting zirconium phosphate powder in nitrogen atmosphere, heating to 550 ℃, and reacting for 7h to obtain layered zirconium phosphate; mixing the layered zirconium phosphate and Mg (NO)3)2·6H2O、Al(NO3)3·9H2Adding O into water, performing ultrasonic treatment for 20min, wherein the ultrasonic frequency is 20kHz, the ultrasonic power is 500W, and the layered zirconium phosphate and Mg (NO) are added3)2·6H2O、Al(NO3)3·9H2Heating the mixture to 80 ℃ and adjusting the pH to 10 by using 3mol/L sodium hydroxide aqueous solution, keeping the temperature of 80 ℃ for reaction for 6 hours, centrifuging to obtain precipitate, and drying to obtain zirconium phosphate intercalation magnalium layered double hydroxide; adding zirconium phosphate intercalation magnalium layered double hydroxide and gamma-glycidyl ether oxypropyl trimethoxy silane into water, uniformly mixing, heating to 80 ℃ for reaction for 4h, then adding functional additives, keeping the temperature of 80 ℃ for reaction for 8h, centrifuging, taking precipitate, and drying to obtain the functionalized zirconium phosphate, wherein the mass ratio of the zirconium phosphate intercalation magnalium layered double hydroxide, the gamma-glycidyl ether oxypropyl trimethoxy silane, the functional additives to the water is 7:2:4: 20. The functional auxiliary agent is a mixture of melamine cyanurate and ammonium polyphosphate in a mass ratio of 2: 3.
A preparation method of a polyethylene cable material with fireproof and flame-retardant functions comprises the following steps: adding polyethylene, PBT resin, ethylene-methyl acrylate copolymer, maleic anhydride grafted ethylene-octene copolymer, beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate, coumarone resin, zinc stearate, trimethylolpropane triacrylate, didecyl phthalate and functionalized zirconium phosphate into an internal mixer, mixing and banburying for 30min, adding into a double-screw extruder, and extruding and granulating at 120 ℃ to obtain the polyethylene cable material with the fireproof and flame-retardant functions.
Example 3
A polyethylene cable material with fireproof and flame-retardant functions is composed of the following raw materials in parts by weight: 40 parts of polyethylene, 25 parts of PBT resin, 20 parts of ethylene-methyl acrylate copolymer, 15 parts of maleic anhydride grafted ethylene-octene copolymer, 2 parts of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate, 6 parts of coumarone resin, 3 parts of zinc stearate, 5 parts of trimethylolpropane triacrylate, 3 parts of didecyl phthalate and 10 parts of functionalized zirconium phosphate.
The preparation method of the functionalized zirconium phosphate comprises the following steps: mixing zirconium phosphate and water according to a mass ratio of 1:30, carrying out ultrasonic treatment for 60min, wherein the ultrasonic frequency is 20kHz, the ultrasonic power is 500W, centrifuging, taking precipitate, and drying to obtain pretreated zirconium phosphate; adding the pretreated zirconium phosphate into a ball mill, and ball-milling for 20 hours at the speed of 600r/min to obtain zirconium phosphate powder; putting zirconium phosphate powder in nitrogen atmosphere, heating to 550 ℃, and reacting for 7h to obtain layered zirconium phosphate; mixing the layered zirconium phosphate and Mg (NO)3)2·6H2O、Al(NO3)3·9H2Adding O into water, performing ultrasonic treatment for 20min, wherein the ultrasonic frequency is 20kHz, the ultrasonic power is 500W, and the layered zirconium phosphate and Mg (NO) are added3)2·6H2O、Al(NO3)3·9H2Heating the mixture to 80 ℃ and adjusting the pH to 10 by using 3mol/L sodium hydroxide aqueous solution, keeping the temperature of 80 ℃ for reaction for 6 hours, centrifuging to obtain precipitate, and drying to obtain zirconium phosphate intercalation magnalium layered double hydroxide; adding zirconium phosphate intercalation magnalium layered double hydroxide and gamma-glycidyl ether oxypropyl trimethoxy silane into water, uniformly mixing, heating to 80 ℃ for reaction for 4h, then adding functional additives, keeping the temperature of 80 ℃ for reaction for 8h, centrifuging, taking precipitate, and drying to obtain the functionalized zirconium phosphate, wherein the mass ratio of the zirconium phosphate intercalation magnalium layered double hydroxide, the gamma-glycidyl ether oxypropyl trimethoxy silane, the functional additives to the water is 7:2:4: 20. The functional assistant is melamine cyanurate.
A preparation method of a polyethylene cable material with fireproof and flame-retardant functions comprises the following steps: adding polyethylene, PBT resin, ethylene-methyl acrylate copolymer, maleic anhydride grafted ethylene-octene copolymer, beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate, coumarone resin, zinc stearate, trimethylolpropane triacrylate, didecyl phthalate and functionalized zirconium phosphate into an internal mixer, mixing and banburying for 30min, adding into a double-screw extruder, and extruding and granulating at 120 ℃ to obtain the polyethylene cable material with the fireproof and flame-retardant functions.
Example 4
A polyethylene cable material with fireproof and flame-retardant functions is composed of the following raw materials in parts by weight: 40 parts of polyethylene, 25 parts of PBT resin, 20 parts of ethylene-methyl acrylate copolymer, 15 parts of maleic anhydride grafted ethylene-octene copolymer, 2 parts of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate, 6 parts of coumarone resin, 3 parts of zinc stearate, 5 parts of trimethylolpropane triacrylate, 3 parts of didecyl phthalate and 10 parts of functionalized zirconium phosphate.
The preparation method of the functionalized zirconium phosphate comprises the following steps: mixing zirconium phosphate and water according to a mass ratio of 1:30, carrying out ultrasonic treatment for 60min, wherein the ultrasonic frequency is 20kHz, the ultrasonic power is 500W, centrifuging, taking precipitate, and drying to obtain pretreated zirconium phosphate; adding the pretreated zirconium phosphate into a ball mill, and ball-milling for 20 hours at the speed of 600r/min to obtain zirconium phosphate powder; putting zirconium phosphate powder in nitrogen atmosphere, heating to 550 ℃, and reacting for 7h to obtain layered zirconium phosphate; mixing the layered zirconium phosphate and Mg (NO)3)2·6H2O、Al(NO3)3·9H2Adding O into water, performing ultrasonic treatment for 20min, wherein the ultrasonic frequency is 20kHz, the ultrasonic power is 500W, and the layered zirconium phosphate and Mg (NO) are added3)2·6H2O、Al(NO3)3·9H2Heating the mixture to 80 ℃ and adjusting the pH to 10 by using 3mol/L sodium hydroxide aqueous solution, keeping the temperature of 80 ℃ for reaction for 6 hours, centrifuging to obtain precipitate, and drying to obtain zirconium phosphate intercalation magnalium layered double hydroxide; adding zirconium phosphate intercalation magnalium layered double hydroxide and gamma-glycidyl ether oxygen propyl trimethoxy silane into water for mixingUniformly mixing, heating to 80 ℃ for reaction for 4h, then adding a functional additive, keeping the temperature of 80 ℃ for reaction for 8h, centrifuging, taking precipitate, and drying to obtain the functionalized zirconium phosphate, wherein the mass ratio of the zirconium phosphate intercalation magnalium layered double hydroxide, the gamma-glycidyl ether oxypropyl trimethoxy silane, the functional additive and the water is 7:2:4: 20. The functional auxiliary agent is ammonium polyphosphate.
A preparation method of a polyethylene cable material with fireproof and flame-retardant functions comprises the following steps: adding polyethylene, PBT resin, ethylene-methyl acrylate copolymer, maleic anhydride grafted ethylene-octene copolymer, beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate, coumarone resin, zinc stearate, trimethylolpropane triacrylate, didecyl phthalate and functionalized zirconium phosphate into an internal mixer, mixing and banburying for 30min, adding into a double-screw extruder, and extruding and granulating at 120 ℃ to obtain the polyethylene cable material with the fireproof and flame-retardant functions.
Example 5
Essentially the same as example 4, except that: the preparation method of the functionalized zirconium phosphate comprises the following steps: mixing zirconium phosphate and Mg (NO)3)2·6H2O、Al(NO3)3·9H2Adding O into water, performing ultrasonic treatment for 20min, wherein the ultrasonic frequency is 20kHz, the ultrasonic power is 500W, and the zirconium phosphate and Mg (NO) are added3)2·6H2O、Al(NO3)3·9H2Heating the mixture to 80 ℃ and adjusting the pH to 10 by using 3mol/L sodium hydroxide aqueous solution, keeping the temperature of 80 ℃ for reaction for 6 hours, centrifuging to obtain precipitate, and drying to obtain zirconium phosphate intercalation magnalium layered double hydroxide; adding zirconium phosphate intercalation magnalium layered double hydroxide and gamma-glycidyl ether oxypropyl trimethoxy silane into water, uniformly mixing, heating to 80 ℃ for reaction for 4h, then adding functional additives, keeping the temperature of 80 ℃ for reaction for 8h, centrifuging, taking precipitate, and drying to obtain the functionalized zirconium phosphate, wherein the mass ratio of the zirconium phosphate intercalation magnalium layered double hydroxide, the gamma-glycidyl ether oxypropyl trimethoxy silane, the functional additives to the water is 7:2:4: 20. The functional auxiliary agent is ammonium polyphosphate.
Example 6
Essentially the same as example 4, except that: the preparation method of the functionalized zirconium phosphate comprises the following steps: mixing zirconium phosphate and water according to a mass ratio of 1:30, carrying out ultrasonic treatment for 60min, wherein the ultrasonic frequency is 20kHz, the ultrasonic power is 500W, centrifuging, taking precipitate, and drying to obtain pretreated zirconium phosphate; adding the pretreated zirconium phosphate into a ball mill, and ball-milling for 20 hours at the speed of 600r/min to obtain zirconium phosphate powder; putting zirconium phosphate powder in nitrogen atmosphere, heating to 550 ℃, and reacting for 7h to obtain layered zirconium phosphate; adding layered zirconium phosphate and gamma-glycidyl ether oxypropyl trimethoxy silane into water, uniformly mixing, heating to 80 ℃ for reaction for 4 hours, then adding a functional aid, keeping the temperature of 80 ℃ for reaction for 8 hours, centrifuging to obtain a precipitate, and drying to obtain the functionalized zirconium phosphate, wherein the mass ratio of the layered zirconium phosphate to the gamma-glycidyl ether oxypropyl trimethoxy silane to the functional aid to the water is 7:2:4: 20. The functional auxiliary agent is ammonium polyphosphate.
Example 7
Essentially the same as example 4, except that: the preparation method of the functionalized zirconium phosphate comprises the following steps: mixing zirconium phosphate and water according to a mass ratio of 1:30, carrying out ultrasonic treatment for 60min, wherein the ultrasonic frequency is 20kHz, the ultrasonic power is 500W, centrifuging, taking precipitate, and drying to obtain pretreated zirconium phosphate; adding the pretreated zirconium phosphate into a ball mill, and ball-milling for 20 hours at the speed of 600r/min to obtain zirconium phosphate powder; putting zirconium phosphate powder in nitrogen atmosphere, heating to 550 ℃, and reacting for 7h to obtain layered zirconium phosphate; mixing the layered zirconium phosphate and Mg (NO)3)2·6H2O、Al(NO3)3·9H2Adding O into water, performing ultrasonic treatment for 20min, wherein the ultrasonic frequency is 20kHz, the ultrasonic power is 500W, and the layered zirconium phosphate and Mg (NO) are added3)2·6H2O、Al(NO3)3·9H2Heating the mixture to 80 ℃ and adjusting the pH to 10 by using 3mol/L sodium hydroxide aqueous solution, keeping the temperature of 80 ℃ for reaction for 6 hours, centrifuging to obtain precipitate, and drying to obtain zirconium phosphate intercalation magnalium layered double hydroxide; adding zirconium phosphate intercalation magnalium layered double hydroxide into waterUniformly mixing, heating to 80 ℃ for reaction for 4h, then adding the functional additive, keeping the temperature of 80 ℃ for reaction for 8h, centrifuging, taking precipitate, and drying to obtain the functionalized zirconium phosphate, wherein the mass ratio of the zirconium phosphate intercalation magnalium layered double hydroxide to the functional additive to water is 7:4: 20. The functional auxiliary agent is ammonium polyphosphate.
Example 8
A polyethylene cable material with fireproof and flame-retardant functions is composed of the following raw materials in parts by weight: 40 parts of ageing-resistant polyethylene master batch, 25 parts of PBT resin, 20 parts of ethylene-methyl acrylate copolymer, 15 parts of maleic anhydride grafted ethylene-octene copolymer, 2 parts of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid octadecyl ester, 6 parts of coumarone resin, 3 parts of zinc stearate, 5 parts of trimethylolpropane triacrylate, 3 parts of didecyl phthalate and 10 parts of functionalized zirconium phosphate.
The preparation method of the aging-resistant polyethylene master batch comprises the following steps:
adding 75 parts by weight of polyethylene, 3.5 parts by weight of nano silicon dioxide, 3 parts by weight of 4-propenyloxy-2-hydroxybenzophenone, 2 parts by weight of didodecyl thiodipropionate and 0.5 part by weight of oleamide into an internal mixer, mixing and banburying for 1.5h, then adding into a double-screw extruder, and extruding and granulating at the extrusion temperature of 125 ℃ to obtain the anti-aging polyethylene master batch.
The preparation method of the functionalized zirconium phosphate comprises the following steps: mixing zirconium phosphate and water according to a mass ratio of 1:30, carrying out ultrasonic treatment for 60min, wherein the ultrasonic frequency is 20kHz, the ultrasonic power is 500W, centrifuging, taking precipitate, and drying to obtain pretreated zirconium phosphate; adding the pretreated zirconium phosphate into a ball mill, and ball-milling for 20 hours at the speed of 600r/min to obtain zirconium phosphate powder; putting zirconium phosphate powder in nitrogen atmosphere, heating to 550 ℃, and reacting for 7h to obtain layered zirconium phosphate; mixing the layered zirconium phosphate and Mg (NO)3)2·6H2O、Al(NO3)3·9H2Adding O into water, performing ultrasonic treatment for 20min, wherein the ultrasonic frequency is 20kHz, the ultrasonic power is 500W, and the layered zirconium phosphate and Mg (NO) are added3)2·6H2O、Al(NO3)3·9H2Heating the mixture to 80 ℃ and adjusting the pH to 10 by using 3mol/L sodium hydroxide aqueous solution, keeping the temperature of 80 ℃ for reaction for 6 hours, centrifuging to obtain precipitate, and drying to obtain zirconium phosphate intercalation magnalium layered double hydroxide; adding zirconium phosphate intercalation magnalium layered double hydroxide and gamma-glycidyl ether oxypropyl trimethoxy silane into water, uniformly mixing, heating to 80 ℃ for reaction for 4h, then adding functional additives, keeping the temperature of 80 ℃ for reaction for 8h, centrifuging, taking precipitate, and drying to obtain the functionalized zirconium phosphate, wherein the mass ratio of the zirconium phosphate intercalation magnalium layered double hydroxide, the gamma-glycidyl ether oxypropyl trimethoxy silane, the functional additives to the water is 7:2:4: 20. The functional auxiliary agent is a mixture of melamine cyanurate and ammonium polyphosphate in a mass ratio of 2: 3.
A preparation method of a polyethylene cable material with fireproof and flame-retardant functions comprises the following steps: adding the aging-resistant polyethylene master batch, the PBT resin, the ethylene-methyl acrylate copolymer, the maleic anhydride grafted ethylene-octene copolymer, beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate, coumarone resin, zinc stearate, trimethylolpropane triacrylate, didecyl phthalate and functionalized zirconium phosphate into an internal mixer, mixing and banburying for 30min, adding into a double-screw extruder, and extruding and granulating at the temperature of 120 ℃ to obtain the polyethylene cable material with the fireproof and flame-retardant functions.
Example 9
A polyethylene cable material with fireproof and flame-retardant functions is composed of the following raw materials in parts by weight: 40 parts of ageing-resistant polyethylene master batch, 25 parts of PBT resin, 20 parts of ethylene-methyl acrylate copolymer, 15 parts of maleic anhydride grafted ethylene-octene copolymer, 2 parts of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid octadecyl ester, 6 parts of coumarone resin, 3 parts of zinc stearate, 5 parts of trimethylolpropane triacrylate, 3 parts of didecyl phthalate and 10 parts of functionalized zirconium phosphate.
The preparation method of the aging-resistant polyethylene master batch comprises the following steps:
mixing methacryloxymethyltriethoxysilane, nano silicon dioxide, nano zirconium dioxide and 85 wt% of isopropanol aqueous solution according to the mass ratio of 3.5:21:7:35 at 50 ℃, carrying out ultrasonic treatment for 0.5h, wherein the ultrasonic frequency is 25kHz and the ultrasonic power is 300W, centrifuging, taking precipitate, and drying to obtain a pretreated inorganic filler; adding 75 parts by weight of polyethylene, 3.5 parts by weight of pretreated inorganic filler, 3 parts by weight of 4-acryloxy-2-hydroxybenzophenone, 2 parts by weight of didodecyl thiodipropionate and 0.5 part by weight of oleamide into an internal mixer, mixing and banburying for 1.5h, then adding into a double-screw extruder, and extruding and granulating at the extrusion temperature of 125 ℃ to obtain the anti-aging polyethylene master batch.
The preparation method of the functionalized zirconium phosphate comprises the following steps: mixing zirconium phosphate and water according to a mass ratio of 1:30, carrying out ultrasonic treatment for 60min, wherein the ultrasonic frequency is 20kHz, the ultrasonic power is 500W, centrifuging, taking precipitate, and drying to obtain pretreated zirconium phosphate; adding the pretreated zirconium phosphate into a ball mill, and ball-milling for 20 hours at the speed of 600r/min to obtain zirconium phosphate powder; putting zirconium phosphate powder in nitrogen atmosphere, heating to 550 ℃, and reacting for 7h to obtain layered zirconium phosphate; mixing the layered zirconium phosphate and Mg (NO)3)2·6H2O、Al(NO3)3·9H2Adding O into water, performing ultrasonic treatment for 20min, wherein the ultrasonic frequency is 20kHz, the ultrasonic power is 500W, and the layered zirconium phosphate and Mg (NO) are added3)2·6H2O、Al(NO3)3·9H2Heating the mixture to 80 ℃ and adjusting the pH to 10 by using 3mol/L sodium hydroxide aqueous solution, keeping the temperature of 80 ℃ for reaction for 6 hours, centrifuging to obtain precipitate, and drying to obtain zirconium phosphate intercalation magnalium layered double hydroxide; adding zirconium phosphate intercalation magnalium layered double hydroxide and gamma-glycidyl ether oxypropyl trimethoxy silane into water, uniformly mixing, heating to 80 ℃ for reaction for 4h, then adding functional additives, keeping the temperature of 80 ℃ for reaction for 8h, centrifuging, taking precipitate, and drying to obtain the functionalized zirconium phosphate, wherein the mass ratio of the zirconium phosphate intercalation magnalium layered double hydroxide, the gamma-glycidyl ether oxypropyl trimethoxy silane, the functional additives to the water is 7:2:4: 20. The functional auxiliary agent is a mixture of melamine cyanurate and ammonium polyphosphate in a mass ratio of 2:3。
A preparation method of a polyethylene cable material with fireproof and flame-retardant functions comprises the following steps: adding the aging-resistant polyethylene master batch, the PBT resin, the ethylene-methyl acrylate copolymer, the maleic anhydride grafted ethylene-octene copolymer, beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate, coumarone resin, zinc stearate, trimethylolpropane triacrylate, didecyl phthalate and functionalized zirconium phosphate into an internal mixer, mixing and banburying for 30min, adding into a double-screw extruder, and extruding and granulating at the temperature of 120 ℃ to obtain the polyethylene cable material with the fireproof and flame-retardant functions.
Test example 1
The polyethylene cable material test samples with fireproof and flame retardant functions prepared in examples 1-4 and 7 are all subjected to compression molding by an XLB-25 type hydraulic press vulcanizer at the temperature of 170 ℃ and under the pressure of 10 MPa.
And (3) testing mechanical properties: the polyethylene cable materials having flame retardant function prepared in examples 1 to 4 and example 7 were subjected to mechanical property test with reference to GB/T1040.2-2006 test conditions for tensile Properties of plastics, part 2: molded and extruded plastics, wherein the dimensions of the sample bars were 2mm 5A type, parallel to 7 groups, and the average value was taken.
TABLE 1 mechanical Property test of polyethylene Cable Material with fireproof and flame retardant function
| Tensile strength/MPa | Elongation at break/% | |
| Example 1 | 11.8 | 177 |
| Example 2 | 14.1 | 203 |
| Example 3 | 13.8 | 201 |
| Example 4 | 13.7 | 197 |
| Example 7 | 13.2 | 191 |
The mechanical properties of example 2 are significantly better than those of examples 3-4, as shown by the comparison of examples 2-4, which may be due to: the zirconium phosphate and the magnesium-aluminum layered double hydroxide mutually improve the agglomeration problem of the zirconium phosphate and the magnesium-aluminum layered double hydroxide in the cable material, are beneficial to the compatibility and the dispersibility of the zirconium phosphate intercalation magnesium-aluminum layered double hydroxide in the cable material, and simultaneously improve the mechanical property of the cable material. The functional zirconium phosphate is prepared by grafting melamine cyanurate and ammonium polyphosphate on zirconium phosphate intercalation magnesium-aluminum layered double hydroxide through gamma-glycidyl ether oxypropyl trimethoxysilane, and organic matters in the functional zirconium phosphate are easy to have strong interaction with a cable material, so that the dispersion performance of the functional zirconium phosphate in the cable material is improved, and the mechanical property of the cable material is improved.
Test example 2
The tensile strength of the polyethylene cable material before and after the aging test was measured according to the method of test example 1, and the tensile strength retention rate was calculated and averaged for 7 groups.
Aging test: reference is made to GB/T16422.2-2014 Plastic laboratory light Exposure test method part 2: xenon arc lamps testing. The test conditions are as follows: and (5) xenon lamp aging for 2000 h.
TABLE 2 ageing resistance test of polyethylene cable material with fireproof and flame-retardant functions
| Retention ratio of tensile strength/%) | |
| Example 8 | 79.8 |
| Example 9 | 85.2 |
Test example 3
The polyethylene cable material test samples with the fireproof and flame-retardant functions prepared in the examples 1 to 7 are all subjected to compression molding by an XLB-25 type hydraulic press vulcanizer at the temperature of 170 ℃ and under the pressure of 10 MPa.
And (3) testing the flame retardant property: reference is made to GB/T2406.2-2009 section 2 for determination of the burning behaviour of plastics by oxygen index method: room temperature test the flame retardant property test of the polyethylene cable material with fireproof and flame retardant functions prepared in examples 1-7, wherein the dimensions of the sample strip are as follows: 80mm by 10mm by 4mm, parallel to 7 groups, and averaged.
TABLE 3 flame retardancy test of polyethylene cable material with fireproof and flame retardant functions
It can be seen from the comparison of example 1 with example 2 that the flame retardant performance of the added functionalized zirconium phosphate is significantly better than that of the added zirconium phosphate. The possible reasons for this are: the functional zirconium phosphate is carbonized at high temperature by melamine cyanurate in the combustion process, oxygen is blocked to improve the flame retardant property, ammonium polyphosphate can be decomposed into phosphoric acid in the combustion process and forms a carbon layer on the surface of a cable material, the melamine cyanurate and the ammonium polyphosphate act synergistically to obviously improve the flame retardant property of the cable material and simultaneously improve the mechanical property of the cable material.
It was found by comparing examples 2 to 4 that the flame retardant properties of example 2 with the simultaneous addition of melamine cyanurate and ammonium polyphosphate were significantly better than those of either melamine cyanurate or ammonium polyphosphate alone, probably because: the functional zirconium phosphate is carbonized at high temperature by melamine cyanurate in the combustion process, oxygen is blocked to improve the flame retardant property, ammonium polyphosphate can be decomposed into phosphoric acid in the combustion process and forms a carbon layer on the surface of a cable material, the melamine cyanurate and the ammonium polyphosphate act synergistically to obviously improve the flame retardant property of the cable material and simultaneously improve the mechanical property of the cable material.
It was found by comparing example 4 with example 5 that the flame retardant performance of example 4 was better than that of example 5. The possible reasons for this are: the layered zirconium phosphate prepared by ball milling, ultrasonic treatment and high-temperature calcination of zirconium phosphate has the advantages of improving the specific surface area, increasing more active sites and further improving the flame retardant property of the cable material.
It was found by comparing example 4 with example 6 that the flame retardant performance of example 4 was better than that of example 6. The possible reasons for this are: preparing laminated zirconium phosphate and Mg (NO) by ball milling, ultrasonic and high-temperature calcining zirconium phosphate3)2·6H2O、Al(NO3)3·9H2The O reaction is used for preparing the zirconium phosphate intercalation magnalium layered double hydroxide, the zirconium phosphate has good surface carbonization and graphitization performance in the cable material, and water generated in the combustion process and the gasification process of the magnalium layered double hydroxide partially remove heat to achieve the flame retardant effect.
The flame retardant performance of example 4 was found to be better than that of example 8 by comparing example 4 with example 7. The possible reasons for this are: melamine cyanurate and ammonium polyphosphate are grafted on zirconium phosphate intercalation magnalium layered double hydroxide through gamma-glycidyl ether oxypropyl trimethoxysilane to prepare functional zirconium phosphate, so that the dispersibility of the zirconium phosphate intercalation magnalium layered double hydroxide is improved; on the other hand, melamine cyanurate and ammonium polyphosphate are grafted on zirconium phosphate intercalation magnalium layered double hydroxide through gamma-glycidyl ether oxypropyl trimethoxysilane, so that the cable material has lasting flame retardant property.
Claims (7)
1. The utility model provides a polyethylene cable material with fire prevention fire-retardant function which characterized in that: the composition is characterized by comprising the following raw materials in parts by weight: 35-45 parts of polyethylene or aging-resistant polyethylene master batch, 15-25 parts of PBT resin, 10-20 parts of ethylene-methyl acrylate copolymer, 5-15 parts of maleic anhydride grafted ethylene-octene copolymer, 1-2 parts of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate, 3-8 parts of coumarone resin, 2-4 parts of zinc stearate, 1-10 parts of trimethylolpropane triacrylate, 1-5 parts of didecyl phthalate, and 5-15 parts of zirconium phosphate or functionalized zirconium phosphate.
2. The polyethylene cable material with fireproof and flame-retardant functions as claimed in claim 1, wherein: the preparation method of the aging-resistant polyethylene master batch comprises the following steps:
mixing methacryloxymethyltriethoxysilane, nano silicon dioxide, nano zirconium dioxide and 75-90 wt% of isopropanol aqueous solution according to the mass ratio of (3-5) to (20-25) to (5-10) to (30-50) at 40-60 ℃, carrying out ultrasonic treatment for 0.5-1h, wherein the ultrasonic frequency is 20-40kHz, the ultrasonic power is 300-500W, centrifuging, taking precipitate, and drying to obtain the pretreated inorganic filler; 70-80 parts of polyethylene, 3-5 parts of pretreatment inorganic filler, 3-5 parts of 4-acryloxy-2-hydroxybenzophenone, 1-3 parts of dilauryl thiodipropionate and 0.1-0.6 part of oleamide by weight are added into an internal mixer to be mixed and banned for 1-2 hours, and then the mixture is added into a double-screw extruder to be extruded and granulated, wherein the extrusion temperature is 110-130 ℃, and the anti-aging polyethylene master batch is obtained.
3. The polyethylene cable material with fireproof and flame-retardant functions as claimed in claim 1, wherein: the preparation method of the functionalized zirconium phosphate comprises the following steps:
mixing zirconium phosphate and water according to the mass ratio of 1 (20-50), carrying out ultrasonic treatment for 30-60min, wherein the ultrasonic frequency is 20-30kHz, the ultrasonic power is 500-; adding the pretreated zirconium phosphate into a ball mill, and ball-milling for 18-24h at the speed of 500-1500r/min to obtain zirconium phosphate powder; putting zirconium phosphate powder in a nitrogen atmosphere, heating to 400-600 ℃, and reacting for 3-7h to obtain layered zirconium phosphate; mixing the layered zirconium phosphate and Mg (NO)3)2·6H2O、Al(NO3)3·9H2Adding O into water for ultrasonic treatment for 10-30min, wherein the ultrasonic frequency is 20-30kHz, the ultrasonic power is 500-1000W, heating to 70-90 ℃, simultaneously adjusting the pH to 9-10 by adopting 2-4mol/L sodium hydroxide aqueous solution, keeping the temperature of 70-90 ℃ for reaction for 3-6h, centrifuging, taking precipitate, and drying to obtain zirconium phosphate intercalation magnalium layered double hydroxide; adding zirconium phosphate intercalation magnalium layered double hydroxide and gamma-glycidyl ether oxypropyl trimethoxy silane into water, uniformly mixing, heating to 60-80 ℃, reacting for 2-4h, then adding functional auxiliary agent, reacting for 5-10h at 70-90 ℃, centrifuging, taking precipitate, and drying to obtain the functionalized zirconium phosphate.
4. The polyethylene cable material with fireproof and flame-retardant functions as claimed in claim 3, wherein: the layered zirconium phosphate, Mg (NO)3)2·6H2O、Al(NO3)3·9H2The mass ratio of O to water is (2-4): (0.5-1): (1-2): (15-30).
5. The polyethylene cable material with fireproof and flame-retardant functions as claimed in claim 3, wherein: the mass ratio of the zirconium phosphate intercalation magnalium layered double hydroxide, the gamma-glycidyl ether oxypropyl trimethoxy silane, the functional auxiliary agent and the water is (3-7): 1-3): 2-5): 10-20.
6. The polyethylene cable material with fireproof and flame-retardant functions as claimed in claim 3, wherein: the functional assistant is one or a mixture of melamine cyanurate and ammonium polyphosphate.
7. The preparation method of the polyethylene cable material with fireproof and flame retardant functions as claimed in any one of claims 1 to 6, wherein the preparation method comprises the following steps: the method comprises the following steps:
adding polyethylene or aging-resistant polyethylene master batch, PBT resin, ethylene-methyl acrylate copolymer, maleic anhydride grafted ethylene-octene copolymer, beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate, coumarone resin, zinc stearate, trimethylolpropane triacrylate, didecyl phthalate, zirconium phosphate or functionalized zirconium phosphate into an internal mixer, mixing and banburying for 20-30min, and then adding into a double-screw extruder for extrusion and granulation, wherein the temperature of the extrusion and granulation is 100-130 ℃, so as to obtain the polyethylene cable material with the fireproof and flame-retardant functions.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116731414A (en) * | 2023-04-13 | 2023-09-12 | 上海滩泰科技有限公司 | Flame-retardant polymer material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116731414A (en) * | 2023-04-13 | 2023-09-12 | 上海滩泰科技有限公司 | Flame-retardant polymer material |
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