CN115948005B - PVC cable material with flame retardant property and preparation method thereof - Google Patents

PVC cable material with flame retardant property and preparation method thereof Download PDF

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CN115948005B
CN115948005B CN202211179847.1A CN202211179847A CN115948005B CN 115948005 B CN115948005 B CN 115948005B CN 202211179847 A CN202211179847 A CN 202211179847A CN 115948005 B CN115948005 B CN 115948005B
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flame retardant
stirring
yttrium
magnesium
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CN115948005A (en
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张燕军
赖楚宇
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Shenzhen Xinantai New Material Co ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

The invention belongs to the technical field of cable materials, and particularly relates to a PVC cable material with flame retardant property and a preparation method thereof. The PVC cable material comprises the following components in parts by weight: 100-120 parts of PVC resin and 40-60 parts of plasticizer; 15-24 parts of filler, 5-15 parts of flame retardant, 5-10 parts of antioxidant, 2-4 parts of lubricant and 3-6 parts of stabilizer; the filler is modified TiO 2 Nanofibers and silicon nitride nanofibers; the modifier for modification is tetra-n-butyl phosphine bromide; the flame retardant is toluene diphenyl phosphate and butyl stannate intercalated yttrium and cerium modified magnesium-iron hydrotalcite; the mass ratio of the toluene diphenyl phosphate to the butyl stannate intercalation yttrium to the cerium modified magnesium-iron hydrotalcite is 1:2-4. The PVC cable material prepared by the invention has excellent flame retardant property and mechanical property.

Description

PVC cable material with flame retardant property and preparation method thereof
Technical Field
The invention belongs to the technical field of cable materials. More particularly, it relates to a PVC cable material with flame retardant property and a preparation method thereof.
Background
Polyvinyl chloride (PVC), which is a commonly used plastic material, has good workability, durability, and electrical insulation, and is widely used in cable materials. Normally, the higher chlorine content in the PVC imparts a certain flame retardancy, but the flame retardancy is affected by the addition of plasticizers and binders during the PVC manufacturing process. In addition, long external radiation causes aging of the PVC material, thereby affecting its flame retardant properties. Therefore, there is a need to develop an effective flame retardant coating to improve the flame retardant properties of PVC plastic cables.
In order to obtain a cable coating with higher flame retardant property, researchers develop a plurality of high-performance flame retardants by researching the influence of different coating materials on the flame retardant property of PVC plastic cables, wherein the flame retardants comprise metal hydrate, inorganic phosphorus flame retardant, organosilicon compound, metal compound and the like. Liu Lihua and the like synthesize the cable composite material with higher flame retardant property through superfine magnesium hydroxide, and the Limiting Oxygen Index (LOI) of the cable composite material can reach 34 percent at most. Gao Suliang and the like, a triazine char former and ammonium polyphosphate are compounded and added to polypropylene to obtain a flame-retardant cable material having an LOI of 30% or more. Namely, the flame retardant property of the PVC plastic cable can be improved by adding the flame retardant material.
CN111019269B discloses a PVC cable material and a preparation method thereof. The PVC cable material comprises the following components in parts by weight: 90-110 parts of PVC resin, 30-50 parts of dioctyl terephthalate, 5-20 parts of epoxidized soybean oil, 10-20 parts of filler, 1-10 parts of organic flame retardant, 1-10 parts of inorganic flame retardant, 3-6 parts of main antioxidant, 3-6 parts of auxiliary antioxidant, 1-5 parts of lubricant and 1-5 parts of stabilizer. The components in the PVC cable material are matched with each other to realize synergistic interaction, so that the smoke suppression flame retardance of the cable material is effectively improved, the mechanical strength of the cable material can be improved, the mechanical damage is effectively reduced, and the service life of the cable is prolonged.
CN111269506a discloses a sun-proof high flame-retardant polyvinyl chloride cable material, which comprises the following raw materials in parts by weight: 40-50 parts of polyvinyl chloride, 10-20 parts of sodium dodecyl sulfate, 5-10 parts of methyl vinyl silicone rubber, 3-6 parts of rice fatty acid polyester, 20-30 parts of plasticizer, 20-30 parts of filler, 1-3 parts of composite stabilizer, 0.1-1 part of lubricant, 0.1-1 part of composite flame retardant and 0.1-1 part of ultraviolet absorber; solves the flame-retardant problem and the environmental protection health problem caused by the plasticizer of the cable material, has the characteristics of high flame retardance and sunlight resistance, and has good stability and excellent mechanical property.
CN109486049a discloses a high flame retardant polyvinyl chloride cable material, which comprises the following components in parts by mass: 80-100 parts of polyvinyl chloride, 30-50 parts of EVA resin, 40-60 parts of PVC resin, 0-20 parts of aluminum hydroxide, 30-60 parts of flame retardant, 0-1.0 part of antimony trioxide, 0-1.5 parts of antimony trioxide, 6-8 parts of melamine cyanurate, 3-5 parts of dioctyl phthalate, 3-5 parts of didecyl phthalate, 5-15 parts of calcium carbonate, 0.5-1.0 part of epoxidized soybean oil, 0.1-0.3 part of coupling agent, 0.1-0.4 part of antioxidant and 0.02-0.1 part of stearic acid; the invention reduces the volume of the liquid plasticizer, has high flame retardant property, can be widely used as an insulating layer of communication cables and cable shells, is also beneficial to other applications requiring flame retardant soft PVC, and is nontoxic and easy to implement.
CN104086916B discloses an environment-friendly polyvinyl chloride cable material for a power system and a production method thereof, wherein the raw materials comprise the following components in percentage by mass: 1 to 5 percent of color master batch, 1 to 5 percent of plasticizer, 1 to 5 percent of lubricant, 1 to 5 percent of auxiliary agent, 1 to 10 percent of flame retardant PBT and the balance of polyvinyl chloride. The wire and cable material disclosed by the invention is excellent in flame retardance, and simultaneously has excellent insulativity, mechanical property, ageing resistance and environmental friendliness; the preparation method of the halogen-free flame-retardant wire and cable material has the advantages of simple process, easy operation, high production efficiency and low cost.
In summary, although the polyvinyl chloride cable material is modified to improve the flame retardant property in the prior art, the mechanical property of the polyvinyl chloride cable material is affected on the premise of ensuring the flame retardant property, so that the polyvinyl chloride cable material still has excellent mechanical property on the premise of ensuring the flame retardant property, and the problem still remains to be solved.
Disclosure of Invention
The invention aims to overcome the defects and the shortcomings in the prior art and provide a PVC cable material with flame retardant property and a preparation method thereof. The PVC cable material comprises the following components in parts by weight: 100-120 parts of PVC resin and 40-60 parts of plasticizer; 15-24 parts of filler, 5-15 parts of flame retardant, 5-10 parts of antioxidant, 2-4 parts of lubricant and 3-6 parts of stabilizer; the filler is modified TiO 2 Nanofibers and silicon nitride nanofibers; the modifier for modification is tetra-n-butyl phosphine bromide; the flame retardant is toluene diphenyl phosphate and butyl stannate intercalated yttrium and cerium modified magnesium-iron hydrotalcite; the mass ratio of the toluene diphenyl phosphate to the butyl stannate intercalation yttrium to the cerium modified magnesium-iron hydrotalcite is 1:2-4. The PVC cable material prepared by the invention has excellent flame retardant property and mechanical property.
The invention aims to provide a PVC cable material with flame retardant property.
The invention further aims to provide a preparation method of the PVC cable material with flame retardant property.
The above object of the present invention is achieved by the following technical scheme:
the PVC cable material with the flame retardant property comprises the following components in parts by weight: 100-120 parts of PVC resin and 40-60 parts of plasticizer; 15-24 parts of filler, 5-15 parts of flame retardant, 5-10 parts of antioxidant, 2-4 parts of lubricant and 3-6 parts of stabilizer;
the filler is modified TiO 2 Nanofibers and silicon nitride nanofibers; the modifier for modification is tetra-n-butyl phosphine bromide;
the flame retardant is toluene diphenyl phosphate and butyl stannate intercalated yttrium and cerium modified magnesium-iron hydrotalcite; the mass ratio of the toluene diphenyl phosphate to the butyl stannate intercalation yttrium to the cerium modified magnesium-iron hydrotalcite is 1:2-4.
Preferably, the polymerization degree of the PVC resin is 1800-2000; the antioxidant is at least one of 2, 4-di-tert-butylphenyl-phosphite triester, dilauryl thiodipropionate and distearyl thiodipropionate; the lubricant is at least one of magnesium stearate, calcium stearate, zinc stearate, polyethylene wax, montan wax or paraffin wax; the stabilizer is at least one of dibutyl tin dilaurate, isooctyl dimercaptoacetate di-n-octyl tin, methyl tin mercaptide, butyl tin mercaptide, dibutyl tin dichloride or octyl tin mercaptide.
Preferably, the plasticizer is a tri-valerate and a dioctyl terephthalate, and the mass ratio of the tri-valerate to the dioctyl terephthalate is 1: 3-6.
Preferably, the TiO 2 The length of the nanofiber is 50-90 nm, and the length-diameter ratio is 40-70:1; the length of the silicon nitride fiber is 40-80 nm, and the length-diameter ratio is 30-60: 1, a step of; the TiO 2 The mass ratio of the nanofiber to the silicon nitride nanofiber is 1:0.5-2.5.
Preferably, the modified TiO 2 The preparation method of the nanofiber and the silicon nitride nanofiber comprises the following steps: tiO is mixed with 2 Adding the nanofibers and the silicon nitride nanofibers into an alcohol solution, stirring uniformly to obtain a dispersion liquid, and then adding tetra-n-butyl phosphine bromide into the dispersion liquid In the process, the reaction is carried out under the stirring condition, the reaction temperature is 65-85 ℃ and the reaction time is 6-10 h, and then the modified TiO is obtained by filtering, washing and vacuum drying at 60-80 ℃ for 10-14 h 2 Nanofibers and silicon nitride nanofibers.
Preferably, the TiO 2 The mass ratio of the nanofiber to the silicon nitride nanofiber is 1:0.5-2.5; the TiO 2 The mass ratio of the nanofiber to tetra-n-butyl phosphine bromide is as follows: 1:0.3 to 0.7; the alcohol is ethanol or isobutanol.
Preferably, the preparation method of the butyl stannate intercalation yttrium and cerium modified magnesium-iron hydrotalcite comprises the following steps: adding a magnesium source, an iron source, an yttrium source and a cerium source into deionized water, uniformly stirring to obtain a mixed solution, and slowly dropwise adding an ethanol water solution containing alkali liquor and butyl stannoic acid into the mixed solution under the condition that the pH is 10-12; then heating to 80-100 ℃, reacting for 2-4 hours, then carrying out hydrothermal reaction, wherein the hydrothermal condition is that the reaction is carried out for 4-10 hours at 120-160 ℃, cooling to room temperature, filtering, washing, and vacuum drying at 60-80 ℃ for 6-12 hours to obtain the magnesium-iron hydrotalcite modified by intercalation yttrium of stannate and cerium;
preferably, the molar ratio of the magnesium source to the iron source to the yttrium source to the cerium source is 1:1.5-3.5:0.02-0.04; 0.01 to 0.05; the molar ratio of the alkali to the butyl stannoic acid is 2:1, a step of; the volume ratio of the ethanol to the water is 1:0.2-0.4; the concentration of the alkali is 0.05mol/L, and the concentration of the butyl stannic acid is 0.025mol/L;
Preferably, the magnesium source is at least one of magnesium nitrate, magnesium acetate and magnesium chloride; the iron source is at least one of ferric nitrate, ferric chloride and ferric acetate, and the yttrium source is at least one of yttrium nitrate, yttrium acetate and yttrium chloride; the cerium source is at least one of cerium nitrate, cerium acetate and cerium chloride; the alkali is one of sodium hydroxide and potassium hydroxide.
Based on the preparation method of the PVC cable material with flame retardant property, the preparation method comprises the following steps:
(1) Mixing and stirring PVC resin and plasticizer to obtain mixed slurry; the stirring temperature is 75-85 ℃, the stirring rotating speed is 800-1000 r/min, and the stirring time is 5-10 min;
(2) Adding filler, flame retardant, antioxidant, lubricant and stabilizer into the mixed slurry obtained in the step (1), and mixing and stirring to obtain a mixed material; the stirring temperature is 105-115 ℃, the stirring rotating speed is 1500-2000 r/min, and the stirring time is 20-40 min; then cooling to 50-70 ℃;
(3) And (3) putting the mixture obtained in the step (2) into a double-screw extruder for melt kneading and extruding, wherein the extruding temperature is 175-185 ℃, and granulating to obtain the PVC cable material.
The invention has the following beneficial effects:
(1) The invention relates to TiO modified by tetra-n-butyl phosphine bromide 2 The nanofiber and the silicon nitride nanofiber not only improve the dispersibility of the nanofiber and the silicon nitride nanofiber, but also improve the performances of the cable material, such as flame retardant property and the like;
(2) By adding toluene diphenyl phosphate and butyl stannate intercalated yttrium and cerium modified magnesium-iron hydrotalcite, the performances of the cable material such as flame retardant property and the like are obviously modified by utilizing the interaction between the two.
(3) Through the interaction of the filler and the flame retardant, the performances such as flame retardant property and the like of the cable material are further improved.
(4) The preparation process is simple, raw materials are easy to obtain, and the preparation method has excellent application prospect.
Detailed Description
The present invention is further illustrated below with reference to specific examples, which are not intended to limit the invention in any way. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art.
Reagents and materials used in the following examples are commercially available unless otherwise specified.
Example 1
The PVC cable material with the flame retardant property comprises the following components in parts by weight: 110 parts of PVC resin and 50 parts of plasticizer; 20 parts of filler, 10 parts of flame retardant, 8 parts of antioxidant, 3 parts of lubricant and 5 parts of stabilizer;
The polymerization degree of the PVC resin is 1900;
the plasticizer is glycerol tripentyl ester and dioctyl terephthalate, and the mass ratio of the glycerol tripentyl ester to the dioctyl terephthalate is 1:4.5;
the filler is modified TiO 2 Nanofibers and silicon nitride nanofibers; the modifier for modification is tetra-n-butyl phosphine bromide;
the TiO 2 The length of the nanofiber is 70nm, and the length-diameter ratio is 55:1; the length of the silicon nitride fiber is 60nm, and the length-diameter ratio is 45:1, a step of;
the modified TiO 2 The preparation method of the nanofiber and the silicon nitride nanofiber comprises the following steps:
1g of TiO 2 Adding nanofiber and 1.5g of silicon nitride nanofiber into 15mL of ethanol solution, stirring uniformly to obtain a dispersion liquid, adding 0.5g of tetra-n-butylphosphine bromide into the dispersion liquid, reacting under the stirring condition, wherein the reaction temperature is 75 ℃, the reaction time is 8 hours, filtering, washing, and vacuum drying at 70 ℃ for 12 hours to obtain the modified TiO 2 Nanofibers and silicon nitride nanofibers;
the flame retardant is toluene diphenyl phosphate and butyl stannate intercalated yttrium and cerium modified magnesium-iron hydrotalcite; the mass ratio of the toluene diphenyl phosphate to the butyl stannate intercalated yttrium to the cerium modified magnesium-iron hydrotalcite is 1:3;
The preparation method of the butyl stannate intercalation yttrium and cerium modified magnesium-iron hydrotalcite comprises the following steps:
adding 10mmol of magnesium nitrate, 2.5mmol of ferric nitrate, 0.3mmol of yttrium nitrate and 0.3mmol of cerium nitrate into 50mL of deionized water, uniformly stirring to obtain a mixed solution, then slowly dropwise adding an ethanol water solution containing sodium hydroxide and butyl stannoic acid (the concentration of the sodium hydroxide is 0.05mol/L, the concentration of the butyl stannic acid is 0.025mol/L, and the volume ratio of the ethanol to the water is 1:0.3) into the mixed solution, and adjusting the pH to 11; then heating to 90 ℃ for reaction for 3 hours, then carrying out hydrothermal reaction under the hydrothermal condition of reacting for 7 hours at 140 ℃, cooling to room temperature, filtering, washing, and vacuum drying for 8 hours at 70 ℃ to obtain the magnesium-iron hydrotalcite modified by yttrium and cerium intercalation of stannate;
the antioxidant is 2, 4-di-tert-butylphenyl-phosphite triester;
the lubricant is magnesium stearate;
the stabilizer is dibutyl tin dilaurate;
the preparation method of the PVC cable material with the flame retardant property comprises the following steps:
(1) Mixing and stirring PVC resin and plasticizer to obtain mixed slurry; the stirring temperature is 80 ℃, the stirring rotating speed is 900r/min, and the stirring time is 8min;
(2) Adding filler, flame retardant, antioxidant, lubricant and stabilizer into the mixed slurry obtained in the step (1), and mixing and stirring to obtain a mixed material; the stirring temperature is 110 ℃, the stirring rotating speed is 1800r/min, and the stirring time is 30min; then cooling to 60 ℃;
(3) And (3) putting the mixture obtained in the step (2) into a double-screw extruder for melt kneading and extruding, wherein the extruding temperature is 180 ℃, and granulating to obtain the PVC cable material.
Example 2
The PVC cable material with the flame retardant property comprises the following components in parts by weight: 120 parts of PVC resin and 40 parts of plasticizer; 24 parts of filler, 5 parts of flame retardant, 10 parts of antioxidant, 2 parts of lubricant and 6 parts of stabilizer;
the polymerization degree of the PVC resin is 2000;
the plasticizer is glycerol tripentyl ester and dioctyl terephthalate, and the mass ratio of the glycerol tripentyl ester to the dioctyl terephthalate is 1: 6, preparing a base material;
the filler is modified TiO 2 Nanofibers and silicon nitride nanofibers; the modifier for modification is tetra-n-butyl phosphine bromide;
the TiO 2 The length of the nanofiber is 90nm, and the length-diameter ratio is 70:1; the length of the silicon nitride fiber is 80nm, and the length-diameter ratio is 60:1, a step of;
The modified TiO 2 The preparation method of the nanofiber and the silicon nitride nanofiber comprises the following steps:
1g of TiO 2 Adding nanofiber and 2.5g of silicon nitride nanofiber into 20mL of isobutanol solution, stirring uniformly to obtain a dispersion liquid, adding 0.7g of tetra-n-butylphosphine bromide into the dispersion liquid, reacting under the stirring condition, wherein the reaction temperature is 85 ℃, the reaction time is 6 hours, filtering, washing, and vacuum drying at 80 ℃ for 10 hours to obtain the modified TiO 2 Nanofibers and silicon nitride nanofibers;
the flame retardant is toluene diphenyl phosphate and butyl stannate intercalated yttrium and cerium modified magnesium-iron hydrotalcite; the mass ratio of the toluene diphenyl phosphate to the butyl stannate intercalated yttrium to the cerium modified magnesium-iron hydrotalcite is 1:4;
the preparation method of the butyl stannate intercalation yttrium and cerium modified magnesium-iron hydrotalcite comprises the following steps:
adding 10mmol of magnesium acetate, 35mmol of ferric chloride, 0.2mmol of yttrium acetate and 0.5mmol of cerium acetate into 50mL of deionized water, uniformly stirring to obtain a mixed solution, and then slowly dropwise adding an ethanol aqueous solution containing potassium hydroxide and butylstannoic acid (the concentration of the potassium hydroxide is 0.05mol/L, the concentration of the butylstannic acid is 0.025mol/L, and the volume ratio of the ethanol to the water is 1:0.3) into the mixed solution under the condition of pH 12; then heating to 100 ℃, reacting for 2 hours, then carrying out hydrothermal reaction under the hydrothermal condition of 160 ℃ for 4 hours, cooling to room temperature, filtering, washing, and vacuum drying at 80 ℃ for 6 hours to obtain the magnesium-iron hydrotalcite modified by yttrium and cerium intercalation of stannate;
The antioxidant is dilauryl thiodipropionate;
the lubricant is zinc stearate;
the stabilizer is isooctyl dimercaptoacetate di-n-octyl tin;
the preparation method of the PVC cable material with the flame retardant property comprises the following steps:
(1) Mixing and stirring PVC resin and plasticizer to obtain mixed slurry; the stirring temperature is 80 ℃, the stirring rotating speed is 900r/min, and the stirring time is 8min;
(2) Adding filler, flame retardant, antioxidant, lubricant and stabilizer into the mixed slurry obtained in the step (1), and mixing and stirring to obtain a mixed material; the stirring temperature is 110 ℃, the stirring rotating speed is 1800r/min, and the stirring time is 30min; then cooling to 60 ℃;
(3) And (3) putting the mixture obtained in the step (2) into a double-screw extruder for melt kneading and extruding, wherein the extruding temperature is 180 ℃, and granulating to obtain the PVC cable material.
Example 3
The PVC cable material with the flame retardant property comprises the following components in parts by weight: 100 parts of PVC resin and 60 parts of plasticizer; 15 parts of filler, 15 parts of flame retardant, 5 parts of antioxidant, 4 parts of lubricant and 3 parts of stabilizer;
the polymerization degree of the PVC resin is 1800;
the plasticizer is glycerol tripentyl ester and dioctyl terephthalate, and the mass ratio of the glycerol tripentyl ester to the dioctyl terephthalate is 1:3, a step of;
The filler is modified TiO 2 Nanofibers and silicon nitride nanofibers; the modifier for modification is tetra-n-butyl phosphine bromide;
the TiO 2 The length of the nanofiber is 50nm, and the length-diameter ratio is 40:1; the length of the silicon nitride fiber is 40nm, and the length-diameter ratio is 30:1, a step of;
the modified TiO 2 The preparation method of the nanofiber and the silicon nitride nanofiber comprises the following steps:
1g of TiO 2 Adding the nanofiber and 0.5g of silicon nitride nanofiber into 10mL of ethanol solution, stirring uniformly to obtain a dispersion liquid, adding 0.3g of tetra-n-butylphosphine bromide into the dispersion liquid, reacting under the stirring condition, wherein the reaction temperature is 65 ℃, the reaction time is 10 hours, filtering, washing, and vacuum drying at 60 ℃ for 14 hours to obtain the modified TiO 2 Nanofibers and silicon nitride nanofibers;
the flame retardant is toluene diphenyl phosphate and butyl stannate intercalated yttrium and cerium modified magnesium-iron hydrotalcite; the mass ratio of the toluene diphenyl phosphate to the butyl stannate intercalated yttrium to the cerium modified magnesium-iron hydrotalcite is 1:2;
the preparation method of the butyl stannate intercalation yttrium and cerium modified magnesium-iron hydrotalcite comprises the following steps:
adding 10mmol of magnesium chloride, 15mmol of ferric acetate, 0.4mmol of yttrium chloride and 0.1mmol of cerium chloride into 50mL of deionized water, uniformly stirring to obtain a mixed solution, and then slowly dropwise adding an ethanol aqueous solution containing alkali liquor and butyl stannoic acid (the concentration of sodium hydroxide is 0.05mol/L, the concentration of butyl stannic acid is 0.025mol/L, and the volume ratio of ethanol to water is 1:0.3) into the mixed solution under the condition of pH of 10; then heating to 80 ℃ for reaction for 4 hours, then carrying out hydrothermal reaction under the hydrothermal condition of 120 ℃ for 10 hours, cooling to room temperature, filtering, washing, and vacuum drying at 60 ℃ for 12 hours to obtain the magnesium-iron hydrotalcite modified by yttrium and cerium intercalation of stannate;
The antioxidant is in distearyl thiodipropionate;
the lubricant is paraffin;
the stabilizer is octyl tin mercaptide;
the preparation method of the PVC cable material with the flame retardant property comprises the following steps:
(1) Mixing and stirring PVC resin and plasticizer to obtain mixed slurry; the stirring temperature is 80 ℃, the stirring rotating speed is 900r/min, and the stirring time is 8min;
(2) Adding filler, flame retardant, antioxidant, lubricant and stabilizer into the mixed slurry obtained in the step (1), and mixing and stirring to obtain a mixed material; the stirring temperature is 110 ℃, the stirring rotating speed is 1800r/min, and the stirring time is 30min; then cooling to 60 ℃;
(3) And (3) putting the mixture obtained in the step (2) into a double-screw extruder for melt kneading and extruding, wherein the extruding temperature is 180 ℃, and granulating to obtain the PVC cable material.
Comparative example 1
The PVC cable material with the flame retardant property comprises the following components in parts by weight: 110 parts of PVC resin and 50 parts of plasticizer; 20 parts of filler, 10 parts of flame retardant, 8 parts of antioxidant, 3 parts of lubricant and 5 parts of stabilizer;
the polymerization degree of the PVC resin is 1900;
the plasticizer is glycerol tripentyl ester
The filler is modified TiO 2 Nanofibers and silicon nitride nanofibers; the modifier for modification is tetra-n-butyl phosphine bromide;
the TiO 2 The length of the nanofiber is 70nm, and the length-diameter ratio is 55:1; the length of the silicon nitride fiber is 60nm, and the length-diameter ratio is 45:1, a step of;
the modified TiO 2 The preparation method of the nanofiber and the silicon nitride nanofiber comprises the following steps:
1g of TiO 2 Adding nanofiber and 1.5g of silicon nitride nanofiber into 15mL of ethanol solution, stirring uniformly to obtain a dispersion liquid, adding 0.5g of tetra-n-butylphosphine bromide into the dispersion liquid, reacting under the stirring condition, wherein the reaction temperature is 75 ℃, the reaction time is 8 hours, filtering, washing, and vacuum drying at 70 ℃ for 12 hours to obtain the modified TiO 2 Nanofibers and silicon nitride nanofibers;
the flame retardant is toluene diphenyl phosphate and butyl stannate intercalated yttrium and cerium modified magnesium-iron hydrotalcite; the mass ratio of the toluene diphenyl phosphate to the butyl stannate intercalated yttrium to the cerium modified magnesium-iron hydrotalcite is 1:3;
the preparation method of the butyl stannate intercalation yttrium and cerium modified magnesium-iron hydrotalcite comprises the following steps:
adding 10mmol of magnesium nitrate, 2.5mmol of ferric nitrate, 0.3mmol of yttrium nitrate and 0.3mmol of cerium nitrate into 50mL of deionized water, uniformly stirring to obtain a mixed solution, then slowly dropwise adding an ethanol water solution containing sodium hydroxide and butyl stannoic acid (the concentration of the sodium hydroxide is 0.05mol/L, the concentration of the butyl stannic acid is 0.025mol/L, and the volume ratio of the ethanol to the water is 1:0.3) into the mixed solution, and adjusting the pH to 11; then heating to 90 ℃ for reaction for 3 hours, then carrying out hydrothermal reaction under the hydrothermal condition of reacting for 7 hours at 140 ℃, cooling to room temperature, filtering, washing, and vacuum drying for 8 hours at 70 ℃ to obtain the magnesium-iron hydrotalcite modified by yttrium and cerium intercalation of stannate;
The antioxidant is 2, 4-di-tert-butylphenyl-phosphite triester;
the lubricant is magnesium stearate;
the stabilizer is dibutyl tin dilaurate;
the preparation method of the PVC cable material with the flame retardant property comprises the following steps:
(1) Mixing and stirring PVC resin and plasticizer to obtain mixed slurry; the stirring temperature is 80 ℃, the stirring rotating speed is 900r/min, and the stirring time is 8min;
(2) Adding filler, flame retardant, antioxidant, lubricant and stabilizer into the mixed slurry obtained in the step (1), and mixing and stirring to obtain a mixed material; the stirring temperature is 110 ℃, the stirring rotating speed is 1800r/min, and the stirring time is 30min; then cooling to 60 ℃;
(3) And (3) putting the mixture obtained in the step (2) into a double-screw extruder for melt kneading and extruding, wherein the extruding temperature is 180 ℃, and granulating to obtain the PVC cable material.
Comparative example 2
The PVC cable material with the flame retardant property comprises the following components in parts by weight: 110 parts of PVC resin and 50 parts of plasticizer; 20 parts of filler, 10 parts of flame retardant, 8 parts of antioxidant, 3 parts of lubricant and 5 parts of stabilizer;
the polymerization degree of the PVC resin is 1900;
the plasticizer is dioctyl terephthalate;
The filler is modified TiO 2 Nanofibers and silicon nitride nanofibers; the modifier for modification is tetra-n-butyl phosphine bromide;
the TiO 2 The length of the nanofiber is 70nm, and the length-diameter ratio is 55:1; the length of the silicon nitride fiber is 60nm, and the length-diameter ratio is 45:1, a step of;
the modified TiO 2 The preparation method of the nanofiber and the silicon nitride nanofiber comprises the following steps:
1g of TiO 2 Adding the nanofiber and 1.5g of silicon nitride nanofiber into 15mL of ethanol solution, stirring uniformly to obtain a dispersion liquid, adding 0.5g of tetra-n-butylphosphine bromide into the dispersion liquid, and reacting under the stirring conditionThe reaction temperature is 75 ℃, the reaction time is 8 hours, and then the modified TiO is obtained by filtering, washing and vacuum drying for 12 hours at 70 DEG C 2 Nanofibers and silicon nitride nanofibers;
the flame retardant is toluene diphenyl phosphate and butyl stannate intercalated yttrium and cerium modified magnesium-iron hydrotalcite; the mass ratio of the toluene diphenyl phosphate to the butyl stannate intercalated yttrium to the cerium modified magnesium-iron hydrotalcite is 1:3;
the preparation method of the butyl stannate intercalation yttrium and cerium modified magnesium-iron hydrotalcite comprises the following steps:
adding 10mmol of magnesium nitrate, 2.5mmol of ferric nitrate, 0.3mmol of yttrium nitrate and 0.3mmol of cerium nitrate into 50mL of deionized water, uniformly stirring to obtain a mixed solution, then slowly dropwise adding an ethanol water solution containing sodium hydroxide and butyl stannoic acid (the concentration of the sodium hydroxide is 0.05mol/L, the concentration of the butyl stannic acid is 0.025mol/L, and the volume ratio of the ethanol to the water is 1:0.3) into the mixed solution, and adjusting the pH to 11; then heating to 90 ℃ for reaction for 3 hours, then carrying out hydrothermal reaction under the hydrothermal condition of reacting for 7 hours at 140 ℃, cooling to room temperature, filtering, washing, and vacuum drying for 8 hours at 70 ℃ to obtain the magnesium-iron hydrotalcite modified by yttrium and cerium intercalation of stannate;
The antioxidant is 2, 4-di-tert-butylphenyl-phosphite triester;
the lubricant is magnesium stearate;
the stabilizer is dibutyl tin dilaurate;
the preparation method of the PVC cable material with the flame retardant property comprises the following steps:
(1) Mixing and stirring PVC resin and plasticizer to obtain mixed slurry; the stirring temperature is 80 ℃, the stirring rotating speed is 900r/min, and the stirring time is 8min;
(2) Adding filler, flame retardant, antioxidant, lubricant and stabilizer into the mixed slurry obtained in the step (1), and mixing and stirring to obtain a mixed material; the stirring temperature is 110 ℃, the stirring rotating speed is 1800r/min, and the stirring time is 30min; then cooling to 60 ℃;
(3) And (3) putting the mixture obtained in the step (2) into a double-screw extruder for melt kneading and extruding, wherein the extruding temperature is 180 ℃, and granulating to obtain the PVC cable material.
Comparative example 3
The PVC cable material with the flame retardant property comprises the following components in parts by weight: 110 parts of PVC resin and 50 parts of plasticizer; 20 parts of filler, 10 parts of flame retardant, 8 parts of antioxidant, 3 parts of lubricant and 5 parts of stabilizer;
the polymerization degree of the PVC resin is 1900;
the plasticizer is glycerol tripentyl ester and dioctyl terephthalate, and the mass ratio of the glycerol tripentyl ester to the dioctyl terephthalate is 1:4.5;
The filler is modified TiO 2 A nanofiber; the modifier for modification is tetra-n-butyl phosphine bromide;
the TiO 2 The length of the nanofiber is 70nm, and the length-diameter ratio is 55:1;
the modified TiO 2 The preparation method of the nanofiber comprises the following steps:
1.5g of TiO 2 Adding nanofiber into 15mL of ethanol solution, stirring uniformly to obtain a dispersion liquid, adding 0.5g of tetra-n-butylphosphine bromide into the dispersion liquid, reacting under the stirring condition, wherein the reaction temperature is 75 ℃, the reaction time is 8 hours, filtering, washing, and vacuum drying at 70 ℃ for 12 hours to obtain the modified TiO 2 A nanofiber;
the flame retardant is toluene diphenyl phosphate and butyl stannate intercalated yttrium and cerium modified magnesium-iron hydrotalcite; the mass ratio of the toluene diphenyl phosphate to the butyl stannate intercalated yttrium to the cerium modified magnesium-iron hydrotalcite is 1:3;
the preparation method of the butyl stannate intercalation yttrium and cerium modified magnesium-iron hydrotalcite comprises the following steps:
adding 10mmol of magnesium nitrate, 2.5mmol of ferric nitrate, 0.3mmol of yttrium nitrate and 0.3mmol of cerium nitrate into 50mL of deionized water, uniformly stirring to obtain a mixed solution, then slowly dropwise adding an ethanol water solution containing sodium hydroxide and butyl stannoic acid (the concentration of the sodium hydroxide is 0.05mol/L, the concentration of the butyl stannic acid is 0.025mol/L, and the volume ratio of the ethanol to the water is 1:0.3) into the mixed solution, and adjusting the pH to 11; then heating to 90 ℃ for reaction for 3 hours, then carrying out hydrothermal reaction under the hydrothermal condition of reacting for 7 hours at 140 ℃, cooling to room temperature, filtering, washing, and vacuum drying for 8 hours at 70 ℃ to obtain the magnesium-iron hydrotalcite modified by yttrium and cerium intercalation of stannate;
The antioxidant is 2, 4-di-tert-butylphenyl-phosphite triester;
the lubricant is magnesium stearate;
the stabilizer is dibutyl tin dilaurate;
the preparation method of the PVC cable material with the flame retardant property comprises the following steps:
(1) Mixing and stirring PVC resin and plasticizer to obtain mixed slurry; the stirring temperature is 80 ℃, the stirring rotating speed is 900r/min, and the stirring time is 8min;
(2) Adding filler, flame retardant, antioxidant, lubricant and stabilizer into the mixed slurry obtained in the step (1), and mixing and stirring to obtain a mixed material; the stirring temperature is 110 ℃, the stirring rotating speed is 1800r/min, and the stirring time is 30min; then cooling to 60 ℃;
(3) And (3) putting the mixture obtained in the step (2) into a double-screw extruder for melt kneading and extruding, wherein the extruding temperature is 180 ℃, and granulating to obtain the PVC cable material.
Comparative example 4
The PVC cable material with the flame retardant property comprises the following components in parts by weight: 110 parts of PVC resin and 50 parts of plasticizer; 20 parts of filler, 10 parts of flame retardant, 8 parts of antioxidant, 3 parts of lubricant and 5 parts of stabilizer;
the polymerization degree of the PVC resin is 1900;
the plasticizer is glycerol tripentyl ester and dioctyl terephthalate, and the mass ratio of the glycerol tripentyl ester to the dioctyl terephthalate is 1:4.5;
The filler is modified silicon nitride nanofiber; the modifier for modification is tetra-n-butyl phosphine bromide;
the length of the silicon nitride fiber is 60nm, and the length-diameter ratio is 45:1, a step of;
the preparation method of the modified silicon nitride nanofiber comprises the following steps:
adding 2.5g of silicon nitride nanofiber into 15mL of ethanol solution, stirring uniformly to obtain a dispersion liquid, adding 0.5g of tetra-n-butyl phosphine bromide into the dispersion liquid, reacting under the stirring condition, wherein the reaction temperature is 75 ℃, the reaction time is 8 hours, filtering, washing, and vacuum drying at 70 ℃ for 12 hours to obtain the modified silicon nitride nanofiber;
the flame retardant is toluene diphenyl phosphate and butyl stannate intercalated yttrium and cerium modified magnesium-iron hydrotalcite; the mass ratio of the toluene diphenyl phosphate to the butyl stannate intercalated yttrium to the cerium modified magnesium-iron hydrotalcite is 1:3;
the preparation method of the butyl stannate intercalation yttrium and cerium modified magnesium-iron hydrotalcite comprises the following steps:
adding 10mmol of magnesium nitrate, 2.5mmol of ferric nitrate, 0.3mmol of yttrium nitrate and 0.3mmol of cerium nitrate into 50mL of deionized water, uniformly stirring to obtain a mixed solution, then slowly dropwise adding an ethanol water solution containing sodium hydroxide and butyl stannoic acid (the concentration of the sodium hydroxide is 0.05mol/L, the concentration of the butyl stannic acid is 0.025mol/L, and the volume ratio of the ethanol to the water is 1:0.3) into the mixed solution, and adjusting the pH to 11; then heating to 90 ℃ for reaction for 3 hours, then carrying out hydrothermal reaction under the hydrothermal condition of reacting for 7 hours at 140 ℃, cooling to room temperature, filtering, washing, and vacuum drying for 8 hours at 70 ℃ to obtain the magnesium-iron hydrotalcite modified by yttrium and cerium intercalation of stannate;
The antioxidant is 2, 4-di-tert-butylphenyl-phosphite triester;
the lubricant is magnesium stearate;
the stabilizer is dibutyl tin dilaurate;
the preparation method of the PVC cable material with the flame retardant property comprises the following steps:
(1) Mixing and stirring PVC resin and plasticizer to obtain mixed slurry; the stirring temperature is 80 ℃, the stirring rotating speed is 900r/min, and the stirring time is 8min;
(2) Adding filler, flame retardant, antioxidant, lubricant and stabilizer into the mixed slurry obtained in the step (1), and mixing and stirring to obtain a mixed material; the stirring temperature is 110 ℃, the stirring rotating speed is 1800r/min, and the stirring time is 30min; then cooling to 60 ℃;
(3) And (3) putting the mixture obtained in the step (2) into a double-screw extruder for melt kneading and extruding, wherein the extruding temperature is 180 ℃, and granulating to obtain the PVC cable material.
Comparative example 5
The PVC cable material with the flame retardant property comprises the following components in parts by weight: 110 parts of PVC resin and 50 parts of plasticizer; 20 parts of filler, 10 parts of flame retardant, 8 parts of antioxidant, 3 parts of lubricant and 5 parts of stabilizer;
the polymerization degree of the PVC resin is 1900;
the plasticizer is glycerol tripentyl ester and dioctyl terephthalate, and the mass ratio of the glycerol tripentyl ester to the dioctyl terephthalate is 1:4.5;
The filler is modified TiO 2 Nanofibers and silicon nitride nanofibers; the modifier for modification is tetra-n-butyl phosphine bromide;
the TiO 2 The length of the nanofiber is 70nm, and the length-diameter ratio is 55:1; the length of the silicon nitride fiber is 60nm, and the length-diameter ratio is 45:1, a step of;
the modified TiO 2 The preparation method of the nanofiber and the silicon nitride nanofiber comprises the following steps:
1g of TiO 2 Adding nanofiber and 1.5g of silicon nitride nanofiber into 15mL of ethanol solution, stirring uniformly to obtain a dispersion liquid, adding 0.5g of tetra-n-butylphosphine bromide into the dispersion liquid, reacting under the stirring condition, wherein the reaction temperature is 75 ℃, the reaction time is 8 hours, filtering, washing, and vacuum drying at 70 ℃ for 12 hours to obtain the modified TiO 2 Nanofibers and silicon nitride nanofibers;
the flame retardant is toluene diphenyl phosphate
The antioxidant is 2, 4-di-tert-butylphenyl-phosphite triester;
the lubricant is magnesium stearate;
the stabilizer is dibutyl tin dilaurate;
the preparation method of the PVC cable material with the flame retardant property comprises the following steps:
(1) Mixing and stirring PVC resin and plasticizer to obtain mixed slurry; the stirring temperature is 80 ℃, the stirring rotating speed is 900r/min, and the stirring time is 8min;
(2) Adding filler, flame retardant, antioxidant, lubricant and stabilizer into the mixed slurry obtained in the step (1), and mixing and stirring to obtain a mixed material; the stirring temperature is 110 ℃, the stirring rotating speed is 1800r/min, and the stirring time is 30min; then cooling to 60 ℃;
(3) And (3) putting the mixture obtained in the step (2) into a double-screw extruder for melt kneading and extruding, wherein the extruding temperature is 180 ℃, and granulating to obtain the PVC cable material.
Comparative example 6
The PVC cable material with the flame retardant property comprises the following components in parts by weight: 110 parts of PVC resin and 50 parts of plasticizer; 20 parts of filler, 10 parts of flame retardant, 8 parts of antioxidant, 3 parts of lubricant and 5 parts of stabilizer;
the polymerization degree of the PVC resin is 1900;
the plasticizer is glycerol tripentyl ester and dioctyl terephthalate, and the mass ratio of the glycerol tripentyl ester to the dioctyl terephthalate is 1:4.5;
the filler is modified TiO 2 Nanofibers and silicon nitride nanofibers; the modifier for modification is tetra-n-butyl phosphine bromide;
the TiO 2 The length of the nanofiber is 70nm, and the length-diameter ratio is 55:1; the length of the silicon nitride fiber is 60nm, and the length-diameter ratio is 45:1, a step of;
The modified TiO 2 The preparation method of the nanofiber and the silicon nitride nanofiber comprises the following steps:
1g of TiO 2 Adding the nanofiber and 1.5g of silicon nitride nanofiber into 15mL of ethanol solution, and uniformly stirring to obtain a fractionDispersing liquid, adding 0.5g tetra-n-butyl phosphine bromide into the dispersion liquid, reacting under stirring at 75 ℃ for 8 hours, filtering, washing, and vacuum drying at 70 ℃ for 12 hours to obtain the modified TiO 2 Nanofibers and silicon nitride nanofibers;
the flame retardant is butyl stannate intercalation yttrium and cerium modified magnesium-iron hydrotalcite;
the preparation method of the butyl stannate intercalation yttrium and cerium modified magnesium-iron hydrotalcite comprises the following steps:
adding 10mmol of magnesium nitrate, 2.5mmol of ferric nitrate, 0.3mmol of yttrium nitrate and 0.3mmol of cerium nitrate into 50mL of deionized water, uniformly stirring to obtain a mixed solution, then slowly dropwise adding an ethanol water solution containing sodium hydroxide and butyl stannoic acid (the concentration of the sodium hydroxide is 0.05mol/L, the concentration of the butyl stannic acid is 0.025mol/L, and the volume ratio of the ethanol to the water is 1:0.3) into the mixed solution, and adjusting the pH to 11; then heating to 90 ℃ for reaction for 3 hours, then carrying out hydrothermal reaction under the hydrothermal condition of reacting for 7 hours at 140 ℃, cooling to room temperature, filtering, washing, and vacuum drying for 8 hours at 70 ℃ to obtain the magnesium-iron hydrotalcite modified by yttrium and cerium intercalation of stannate;
The antioxidant is 2, 4-di-tert-butylphenyl-phosphite triester;
the lubricant is magnesium stearate;
the stabilizer is dibutyl tin dilaurate;
the preparation method of the PVC cable material with the flame retardant property comprises the following steps:
(1) Mixing and stirring PVC resin and plasticizer to obtain mixed slurry; the stirring temperature is 80 ℃, the stirring rotating speed is 900r/min, and the stirring time is 8min;
(2) Adding filler, flame retardant, antioxidant, lubricant and stabilizer into the mixed slurry obtained in the step (1), and mixing and stirring to obtain a mixed material; the stirring temperature is 110 ℃, the stirring rotating speed is 1800r/min, and the stirring time is 30min; then cooling to 60 ℃;
(3) And (3) putting the mixture obtained in the step (2) into a double-screw extruder for melt kneading and extruding, wherein the extruding temperature is 180 ℃, and granulating to obtain the PVC cable material.
Comparative example 7
The PVC cable material with the flame retardant property comprises the following components in parts by weight: 110 parts of PVC resin and 50 parts of plasticizer; 20 parts of filler, 10 parts of flame retardant, 8 parts of antioxidant, 3 parts of lubricant and 5 parts of stabilizer;
the polymerization degree of the PVC resin is 1900;
the plasticizer is glycerol tripentyl ester and dioctyl terephthalate, and the mass ratio of the glycerol tripentyl ester to the dioctyl terephthalate is 1:4.5;
The filler is modified TiO 2 Nanofibers and silicon nitride nanofibers; the modifier for modification is tetra-n-butyl phosphine bromide;
the TiO 2 The length of the nanofiber is 70nm, and the length-diameter ratio is 55:1; the length of the silicon nitride fiber is 60nm, and the length-diameter ratio is 45:1, a step of;
the modified TiO 2 The preparation method of the nanofiber and the silicon nitride nanofiber comprises the following steps:
1g of TiO 2 Adding nanofiber and 1.5g of silicon nitride nanofiber into 15mL of ethanol solution, stirring uniformly to obtain a dispersion liquid, adding 0.5g of tetra-n-butylphosphine bromide into the dispersion liquid, reacting under the stirring condition, wherein the reaction temperature is 75 ℃, the reaction time is 8 hours, filtering, washing, and vacuum drying at 70 ℃ for 12 hours to obtain the modified TiO 2 Nanofibers and silicon nitride nanofibers;
the flame retardant is toluene diphenyl phosphate and butyl stannate intercalation yttrium modified magnesium-iron hydrotalcite; the mass ratio of the toluene diphenyl phosphate to the butyl stannate intercalation yttrium modified magnesium-iron hydrotalcite is 1:3;
the preparation method of the butylstannate intercalation yttrium modified magnesium-iron hydrotalcite comprises the following steps:
adding 10mmol of magnesium nitrate, 2.5mmol of ferric nitrate and 0.6mmol of yttrium nitrate into 50mL of deionized water, uniformly stirring to obtain a mixed solution, then slowly dropwise adding an ethanol water solution containing sodium hydroxide and butyl stannoic acid (the concentration of the sodium hydroxide is 0.05mol/L, the concentration of the butyl stannic acid is 0.025mol/L, and the volume ratio of the ethanol to the water is 1:0.3), and adjusting the pH to 11; then heating to 90 ℃ for reaction for 3 hours, then carrying out hydrothermal reaction under the hydrothermal condition of reacting for 7 hours at 140 ℃, cooling to room temperature, filtering, washing, and vacuum drying for 8 hours at 70 ℃ to obtain the intercalated yttrium-modified magnesium-iron hydrotalcite;
The antioxidant is 2, 4-di-tert-butylphenyl-phosphite triester;
the lubricant is magnesium stearate;
the stabilizer is dibutyl tin dilaurate;
the preparation method of the PVC cable material with the flame retardant property comprises the following steps:
(1) Mixing and stirring PVC resin and plasticizer to obtain mixed slurry; the stirring temperature is 80 ℃, the stirring rotating speed is 900r/min, and the stirring time is 8min;
(2) Adding filler, flame retardant, antioxidant, lubricant and stabilizer into the mixed slurry obtained in the step (1), and mixing and stirring to obtain a mixed material; the stirring temperature is 110 ℃, the stirring rotating speed is 1800r/min, and the stirring time is 30min; then cooling to 60 ℃;
(3) And (3) putting the mixture obtained in the step (2) into a double-screw extruder for melt kneading and extruding, wherein the extruding temperature is 180 ℃, and granulating to obtain the PVC cable material.
Comparative example 8
The PVC cable material with the flame retardant property comprises the following components in parts by weight: 110 parts of PVC resin and 50 parts of plasticizer; 20 parts of filler, 10 parts of flame retardant, 8 parts of antioxidant, 3 parts of lubricant and 5 parts of stabilizer;
the polymerization degree of the PVC resin is 1900;
the plasticizer is glycerol tripentyl ester and dioctyl terephthalate, and the mass ratio of the glycerol tripentyl ester to the dioctyl terephthalate is 1:4.5;
The filler is modified TiO 2 Nanofiber and silicon nitride nanoparticleA rice fiber; the modifier for modification is tetra-n-butyl phosphine bromide;
the TiO 2 The length of the nanofiber is 70nm, and the length-diameter ratio is 55:1; the length of the silicon nitride fiber is 60nm, and the length-diameter ratio is 45:1, a step of;
the modified TiO 2 The preparation method of the nanofiber and the silicon nitride nanofiber comprises the following steps:
1g of TiO 2 Adding nanofiber and 1.5g of silicon nitride nanofiber into 15mL of ethanol solution, stirring uniformly to obtain a dispersion liquid, adding 0.5g of tetra-n-butylphosphine bromide into the dispersion liquid, reacting under the stirring condition, wherein the reaction temperature is 75 ℃, the reaction time is 8 hours, filtering, washing, and vacuum drying at 70 ℃ for 12 hours to obtain the modified TiO 2 Nanofibers and silicon nitride nanofibers;
the flame retardant is toluene diphenyl phosphate and butyl stannate intercalation cerium modified magnesium-iron hydrotalcite; the mass ratio of the toluene diphenyl phosphate to the butylstannate intercalation cerium modified magnesium-iron hydrotalcite is 1:3;
the preparation method of the butylstannate intercalation cerium modified magnesium-iron hydrotalcite comprises the following steps:
adding 10mmol of magnesium nitrate, 2.5mmol of ferric nitrate and 0.6mmol of cerium nitrate into 50mL of deionized water, uniformly stirring to obtain a mixed solution, then slowly dropwise adding an ethanol aqueous solution containing sodium hydroxide and butyl stannoic acid (the concentration of the sodium hydroxide is 0.05mol/L, the concentration of the butyl stannic acid is 0.025mol/L, and the volume ratio of the ethanol to the water is 1:0.3), and adjusting the pH to 11; then heating to 90 ℃ for reaction for 3 hours, then carrying out hydrothermal reaction under the hydrothermal condition of reacting for 7 hours at 140 ℃, cooling to room temperature, filtering, washing, and vacuum drying for 8 hours at 70 ℃ to obtain the magnesium-iron hydrotalcite modified by the intercalation cerium of the base stannate;
The antioxidant is 2, 4-di-tert-butylphenyl-phosphite triester;
the lubricant is magnesium stearate;
the stabilizer is dibutyl tin dilaurate;
the preparation method of the PVC cable material with the flame retardant property comprises the following steps:
(1) Mixing and stirring PVC resin and plasticizer to obtain mixed slurry; the stirring temperature is 80 ℃, the stirring rotating speed is 900r/min, and the stirring time is 8min;
(2) Adding filler, flame retardant, antioxidant, lubricant and stabilizer into the mixed slurry obtained in the step (1), and mixing and stirring to obtain a mixed material; the stirring temperature is 110 ℃, the stirring rotating speed is 1800r/min, and the stirring time is 30min; then cooling to 60 ℃;
(3) And (3) putting the mixture obtained in the step (2) into a double-screw extruder for melt kneading and extruding, wherein the extruding temperature is 180 ℃, and granulating to obtain the PVC cable material.
Comparative example 9
The PVC cable material with the flame retardant property comprises the following components in parts by weight: 110 parts of PVC resin and 50 parts of plasticizer; 30 parts of filler, 8 parts of antioxidant, 3 parts of lubricant and 5 parts of stabilizer;
the polymerization degree of the PVC resin is 1900;
the plasticizer is glycerol tripentyl ester and dioctyl terephthalate, and the mass ratio of the glycerol tripentyl ester to the dioctyl terephthalate is 1:4.5;
The filler is modified TiO 2 Nanofibers and silicon nitride nanofibers; the modifier for modification is tetra-n-butyl phosphine bromide;
the TiO 2 The length of the nanofiber is 70nm, and the length-diameter ratio is 55:1; the length of the silicon nitride fiber is 60nm, and the length-diameter ratio is 45:1, a step of;
the modified TiO 2 The preparation method of the nanofiber and the silicon nitride nanofiber comprises the following steps:
1g of TiO 2 Adding nanofiber and 1.5g of silicon nitride nanofiber into 15mL of ethanol solution, stirring uniformly to obtain a dispersion liquid, adding 0.5g of tetra-n-butylphosphine bromide into the dispersion liquid, reacting under the stirring condition, wherein the reaction temperature is 75 ℃, the reaction time is 8 hours, filtering, washing, and vacuum drying at 70 ℃ for 12 hours to obtain the modified TiO 2 Nanofibers and nitrogenSilicon-melting nanofibers;
the antioxidant is 2, 4-di-tert-butylphenyl-phosphite triester;
the lubricant is magnesium stearate;
the stabilizer is dibutyl tin dilaurate;
the preparation method of the PVC cable material with the flame retardant property comprises the following steps:
(1) Mixing and stirring PVC resin and plasticizer to obtain mixed slurry; the stirring temperature is 80 ℃, the stirring rotating speed is 900r/min, and the stirring time is 8min;
(2) Adding filler, antioxidant, lubricant and stabilizer into the mixed slurry obtained in the step (1), and mixing and stirring to obtain a mixed material; the stirring temperature is 110 ℃, the stirring rotating speed is 1800r/min, and the stirring time is 30min; then cooling to 60 ℃;
(3) And (3) putting the mixture obtained in the step (2) into a double-screw extruder for melt kneading and extruding, wherein the extruding temperature is 180 ℃, and granulating to obtain the PVC cable material.
Comparative example 10
The PVC cable material with the flame retardant property comprises the following components in parts by weight: 110 parts of PVC resin and 50 parts of plasticizer; the flame retardant comprises 30 parts of flame retardant, 8 parts of antioxidant, 3 parts of lubricant and 5 parts of stabilizer;
the polymerization degree of the PVC resin is 1900;
the plasticizer is glycerol tripentyl ester and dioctyl terephthalate, and the mass ratio of the glycerol tripentyl ester to the dioctyl terephthalate is 1:4.5;
the flame retardant is toluene diphenyl phosphate and butyl stannate intercalated yttrium and cerium modified magnesium-iron hydrotalcite; the mass ratio of the toluene diphenyl phosphate to the butyl stannate intercalated yttrium to the cerium modified magnesium-iron hydrotalcite is 1:3;
the preparation method of the butyl stannate intercalation yttrium and cerium modified magnesium-iron hydrotalcite comprises the following steps:
Adding 10mmol of magnesium nitrate, 2.5mmol of ferric nitrate, 0.3mmol of yttrium nitrate and 0.3mmol of cerium nitrate into 50mL of deionized water, uniformly stirring to obtain a mixed solution, then slowly dropwise adding an ethanol water solution containing sodium hydroxide and butyl stannoic acid (the concentration of the sodium hydroxide is 0.05mol/L, the concentration of the butyl stannic acid is 0.025mol/L, and the volume ratio of the ethanol to the water is 1:0.3) into the mixed solution, and adjusting the pH to 11; then heating to 90 ℃ for reaction for 3 hours, then carrying out hydrothermal reaction under the hydrothermal condition of reacting for 7 hours at 140 ℃, cooling to room temperature, filtering, washing, and vacuum drying for 8 hours at 70 ℃ to obtain the magnesium-iron hydrotalcite modified by yttrium and cerium intercalation of stannate;
the antioxidant is 2, 4-di-tert-butylphenyl-phosphite triester;
the lubricant is magnesium stearate;
the stabilizer is dibutyl tin dilaurate;
the preparation method of the PVC cable material with the flame retardant property comprises the following steps:
(1) Mixing and stirring PVC resin and plasticizer to obtain mixed slurry; the stirring temperature is 80 ℃, the stirring rotating speed is 900r/min, and the stirring time is 8min;
(2) Adding a flame retardant, an antioxidant, a lubricant and a stabilizer into the mixed slurry obtained in the step (1), and mixing and stirring to obtain a mixed material; the stirring temperature is 110 ℃, the stirring rotating speed is 1800r/min, and the stirring time is 30min; then cooling to 60 ℃;
(3) And (3) putting the mixture obtained in the step (2) into a double-screw extruder for melt kneading and extruding, wherein the extruding temperature is 180 ℃, and granulating to obtain the PVC cable material.
The flame retardant properties and tensile strength of examples 1-3 and comparative examples 1-10 were tested as follows, and the test results are shown in Table 1:
tensile strength: testing was performed according to standard GB/T16421-1996;
limiting Oxygen Index (LOI) test: the sample sizes were 13mm by 6mm by 3mm according to ASTM D2863 standard test.
TABLE 1
Tensile Strength (MPa) Limiting Oxygen Index (LOI) (%)
Example 1 26.75 39.85
Example 2 25.24 37.43
Example 3 26.11 38.56
Comparative example 1 25.15 37.39
Comparative example 2 25.21 37.41
Comparative example 3 24.32 36.15
Comparative example 4 24.53 36.43
Comparative example 5 22.14 36.65
Comparative example 6 25.06 36.86
Comparative example 7 25.22 37.25
Comparative example 8 25.23 37.31
Comparative example 9 24.85 29.83
Comparative example 10 23.63 36.54
As can be seen from Table 1, the PVC cable material with flame retardant property prepared by the invention has excellent flame retardant property and tensile strength by utilizing the interaction between components, and has excellent application prospect.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.

Claims (8)

1. A PVC cable material with flame retardant property is characterized in that: the PVC cable material comprises the following components in parts by weight: 100-120 parts of PVC resin and 40-60 parts of plasticizer; 15-24 parts of filler, 5-15 parts of flame retardant, 5-10 parts of antioxidant, 2-4 parts of lubricant and 3-6 parts of stabilizer;
the filler is modified TiO 2 Nanofibers and silicon nitride nanofibers; the modifier for modification is tetra-n-butyl phosphine bromide;
the flame retardant is toluene diphenyl phosphate and butyl stannate intercalated yttrium and cerium modified magnesium-iron hydrotalcite; the mass ratio of the toluene diphenyl phosphate to the butyl stannate intercalated yttrium to the cerium modified magnesium-iron hydrotalcite is 1:2-4;
the polymerization degree of the PVC resin is 1800-2000; the plasticizer is glyceryl tripentyl ester and dioctyl terephthalate;
the modified TiO 2 The preparation method of the nanofiber and the silicon nitride nanofiber comprises the following steps: tiO is mixed with 2 Adding nanofibers and silicon nitride nanofibers into an alcohol solution, stirring uniformly to obtain a dispersion liquid, adding tetra-n-butylphosphine bromide into the dispersion liquid, reacting under stirring conditions at 65-85 ℃ for 6-10 h, filtering, washing, and vacuum drying at 60-80 ℃ for 10-14 h to obtain the modified TiO 2 Nanofibers and silicon nitride nanofibers; the TiO 2 The mass ratio of the nanofiber to the silicon nitride nanofiber is 1:0.5-2.5; the TiO 2 The mass ratio of the nanofiber to tetra-n-butyl phosphine bromide is as follows: 1:0.3 to 0.7;
the preparation method of the butyl stannate intercalation yttrium and cerium modified magnesium-iron hydrotalcite comprises the following steps: adding a magnesium source, an iron source, an yttrium source and a cerium source into deionized water, uniformly stirring to obtain a mixed solution, and slowly dropwise adding an ethanol water solution containing alkali liquor and butyl stannoic acid into the mixed solution under the condition that the pH is 10-12; then heating to 80-100 ℃, reacting for 2-4 hours, then carrying out hydrothermal reaction, wherein the hydrothermal condition is that the reaction is carried out for 4-10 hours at 120-160 ℃, cooling to room temperature, filtering, washing, and vacuum drying at 60-80 ℃ for 6-12 hours to obtain the magnesium-iron hydrotalcite modified by intercalation yttrium of stannate and cerium; the molar ratio of the magnesium source to the iron source to the yttrium source to the cerium source is 1:1.5-3.5:0.02-0.04; 0.01 to 0.05; the molar ratio of the alkali to the butyl stannoic acid is 2:1.
2. the PVC cable material having flame retardant properties of claim 1, wherein: the antioxidant is at least one of 2, 4-di-tert-butylphenyl-phosphite triester, dilauryl thiodipropionate and distearyl thiodipropionate; the lubricant is at least one of magnesium stearate, calcium stearate, zinc stearate, polyethylene wax, montan wax or paraffin wax; the stabilizer is at least one of dibutyl tin dilaurate, isooctyl dimercaptoacetate di-n-octyl tin, methyl tin mercaptide, butyl tin mercaptide, dibutyl tin dichloride or octyl tin mercaptide.
3. The PVC cable material having flame retardant properties of claim 1, wherein: the mass ratio of the tripentyl glyceride to the dioctyl terephthalate is 1: 3-6.
4. The PVC cable material having flame retardant properties of claim 1, wherein: the TiO 2 The length of the nanofiber is 50-90 nm, and the length-diameter ratio is 40-70:1; the length of the silicon nitride fiber is 40-80 nm, and the length-diameter ratio is 30-60: 1.
5. the PVC cable material having flame retardant properties of claim 1, wherein: the modified TiO 2 In the preparation method of the nanofiber and the silicon nitride nanofiber, the alcohol is ethanol or isobutanol.
6. The PVC cable material having flame retardant properties of claim 1, wherein: in the preparation method of the butyl stannate intercalation yttrium and cerium modified magnesium-iron hydrotalcite, the volume ratio of the ethanol to the water is 1:0.2-0.4; the concentration of the alkali is 0.05mol/L, and the concentration of the butyl stannic acid is 0.025mol/L.
7. The PVC cable material having flame retardant properties of claim 1, wherein: in the preparation method of the butylstannate intercalation yttrium and cerium modified magnesium-iron hydrotalcite, the magnesium source is at least one of magnesium nitrate, magnesium acetate and magnesium chloride; the iron source is at least one of ferric nitrate, ferric chloride and ferric acetate, and the yttrium source is at least one of yttrium nitrate, yttrium acetate and yttrium chloride; the cerium source is at least one of cerium nitrate, cerium acetate and cerium chloride; the alkali is one of sodium hydroxide and potassium hydroxide.
8. The method for producing a PVC cable material having flame retardant properties according to any one of claims 1 to 7, wherein: the preparation method comprises the following steps:
(1) Mixing and stirring PVC resin and plasticizer to obtain mixed slurry; the stirring temperature is 75-85 ℃, the stirring rotating speed is 800-1000 r/min, and the stirring time is 5-10 min;
(2) Adding filler, flame retardant, antioxidant, lubricant and stabilizer into the mixed slurry obtained in the step (1), and mixing and stirring to obtain a mixed material; the stirring temperature is 105-115 ℃, the stirring rotating speed is 1500-2000 r/min, and the stirring time is 20-40 min; then cooling to 50-70 ℃;
(3) And (3) putting the mixture obtained in the step (2) into a double-screw extruder for melt kneading and extruding, wherein the extruding temperature is 175-185 ℃, and granulating to obtain the PVC cable material.
CN202211179847.1A 2022-09-27 2022-09-27 PVC cable material with flame retardant property and preparation method thereof Active CN115948005B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102482472A (en) * 2009-08-24 2012-05-30 Adeka株式会社 Vinyl chloride resin composition for transparent products
CN103756371A (en) * 2013-12-31 2014-04-30 福建师范大学 Preparation method of different acid radical ion mixed and intercalated hydrotalcite flame retardant
CN109206792A (en) * 2018-09-28 2019-01-15 安徽金日包装有限公司 A kind of full-automatic trademark plastering machine PVC material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102482472A (en) * 2009-08-24 2012-05-30 Adeka株式会社 Vinyl chloride resin composition for transparent products
CN103756371A (en) * 2013-12-31 2014-04-30 福建师范大学 Preparation method of different acid radical ion mixed and intercalated hydrotalcite flame retardant
CN109206792A (en) * 2018-09-28 2019-01-15 安徽金日包装有限公司 A kind of full-automatic trademark plastering machine PVC material

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