CN112126202A - High-flame-retardancy color master batch and preparation method thereof - Google Patents
High-flame-retardancy color master batch and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-flame-retardancy color master batch, which comprises the following raw materials in parts by weight: 30-50 parts of flame-retardant PET, 10-20 parts of toner, 15-25 parts of toughening filler, 1-5 parts of dispersant, 1-3 parts of magnesium silicate, 2-5 parts of vitamin E and 6-8 parts of lignocellulose; firstly, sequentially adding flame-retardant PET, toner, toughening filler, dispersant, magnesium silicate, vitamin E and lignocellulose into a high-speed stirring kettle to prepare a mixture; secondly, adding the mixture into a double-screw extruder for blending, transferring the mixture into an internal mixer for internal mixing after the mixing is finished, and then carrying out bracing and granulating treatment to obtain the high-flame-retardancy color master batch; the invention discloses a preparation method of a high-flame-retardancy color master batch; the filler integrating the carbon source, the acid source and the gas source is prepared, so that the problem that the nano particle filler is not easy to disperse is solved, the PET can be endowed with excellent flame retardant property, and the master batch is further endowed with excellent flame retardant property.
Description
Technical Field
The invention belongs to the technical field of color master batch preparation, and particularly relates to a high-flame-retardancy color master batch and a preparation method thereof.
Background
The polyethylene terephthalate (PET) has excellent comprehensive performance and low price, a rigid group exists on the main molecular chain, the molecular chain has high symmetry, and the physical and mechanical properties, the heat resistance, the electrical properties, the film forming property and other properties are excellent. Therefore, PET is widely used in engineering plastics, fiber textiles and film industries; especially in the application of engineering plastics, compared with other traditional engineering plastics, such as Polyamide (PA), Polycarbonate (PC) and the like, the composite material has extremely high cost performance and is very competitive.
Because industries such as electronic appliances, automobiles, household appliances and the like have strict requirements on material combustion and safety performance, the improvement of the flame retardance of the PET material gradually becomes one of the basic requirements of the PET material, so that the PET material has extremely important practical significance in having good flame retardance.
The Chinese invention patent CN103059520A discloses a flame-retardant PET white master batch and a preparation method thereof. The invention provides a flame-retardant PET white master batch and a preparation method thereof, aiming at meeting the requirement of PET materials on safety performance in the application process of industries such as electronic appliances, automobiles, household appliances and the like. The white master batch comprises 30-50% of PET slices, 20-50% of white pigment, 15-45% of flame retardant, 0.1-3% of antioxidant, 0.1-3% of fluorescent whitening agent, 1-10% of dispersing agent and 1-10% of compatilizer, wherein the percentages are weight percentages.
Disclosure of Invention
In order to overcome the technical problems, the invention provides a high-flame-retardancy color master batch and a preparation method thereof.
In the prior art, the nano particle filler, the flame retardant and the PET are directly compounded to endow the PET with flame retardant performance, but the nano particle filler cannot be uniformly dispersed in the PET and the problem of dampness of the flame retardant cannot be solved, so that the nano particle filler, the material A and the material B are mixed according to the weight ratio of 1: 0.05-0.08 in the step S3 and then are melted and mixed with the PET to form the filler integrating the carbon source, the acid source and the gas source, thereby solving the problem that the nano particle filler is not easy to disperse and endowing the PET with excellent flame retardant performance.
The purpose of the invention can be realized by the following technical scheme:
the high-flame-retardancy color master batch comprises the following raw materials in parts by weight: 30-50 parts of flame-retardant PET, 10-20 parts of toner, 15-25 parts of toughening filler, 1-5 parts of dispersant, 1-3 parts of magnesium silicate, 2-5 parts of vitamin E and 6-8 parts of lignocellulose;
the high-flame-retardancy color master batch is prepared by the following method:
firstly, sequentially adding flame-retardant PET, toner, toughening filler, dispersant, magnesium silicate, vitamin E and lignocellulose into a high-speed stirring kettle, and stirring at the rotating speed of 480-;
and secondly, adding the mixture prepared in the first step into a double-screw extruder for blending, controlling the blending temperature to be 200-250 ℃, controlling the screw rotating speed to be 200r/min, transferring the mixture into an internal mixer for internal mixing after the mixing is finished, controlling the internal mixing temperature to be 350-400 ℃, and controlling the internal mixing time to be 20-30min, and then carrying out bracing and granulating treatment to prepare the high-flame-retardancy color master batch.
Further, the toner is any one of phthalocyanine red, phthalocyanine blue and phthalocyanine green, and the dispersant is one or two of stearic acid monoglyceride and polyethylene glycol mixed according to any proportion.
Further, the flame retardant PET is prepared by the following method:
step S1, adding glucose into deionized water, heating in a water bath at 35-40 ℃, stirring for 30min at a rotating speed of 120r/min for 100 plus materials to obtain a glucose solution, transferring the glucose solution into a high-pressure reaction kettle, heating to 300 ℃ at a speed of 5-8 ℃/min, preserving heat for 8h at the temperature, cooling and filtering after finishing preserving heat, washing a filter cake three times by using absolute ethyl alcohol and deionized water respectively, and transferring into a drying box at 80-90 ℃ for drying for 12h to obtain a nanoparticle filler;
step S2, adding salicylaldehyde into a sodium hydroxide aqueous solution with the mass fraction of 10%, uniformly stirring for 15min, transferring to a three-neck flask, heating in a water bath at 35-40 ℃, magnetically stirring for 20min, then dropwise adding a hydrogen peroxide aqueous solution with the mass fraction of 30%, controlling the dropwise adding time to be 30-45min, then heating to 45-50 ℃, continuing stirring for 10min, centrifuging, filtering, transferring to an oven with the temperature of 85-90 ℃ and drying for 4-5h to obtain a material A;
step S3, adding urea and ammonium phosphate into a three-neck flask according to the molar ratio of 1: 1.5-1.8, heating in a water bath at 110 ℃ under 100-;
step S4, mixing the prepared nano particle filler, the material A and the material B according to the weight ratio of 1: 0.05-0.08 to prepare the filler, slicing the PET, drying at 80 ℃ for 10 hours, adding the PET and the filler into a double-screw extruder, melting, extruding and granulating, transferring into a vulcanizing machine, and pressing at the pressure of 20MPa and the temperature of 150 ℃ for 15min to prepare the flame-retardant PET, wherein the weight ratio of the filler to the PET is controlled to be 0.1-0.3: 1.
The glucose solution is prepared in the step S1, heat preservation is carried out for 8 hours at the temperature of 280 plus 300 ℃, a nano particle filler is prepared, the nano particle filler is a carbon material, the surface of the nano particle filler contains a large amount of hydroxyl and carboxyl, so the nano particle filler has large specific surface area, small density and excellent heat stability, in the step S2, salicylaldehyde is firstly added into a sodium hydroxide aqueous solution, then a hydrogen peroxide aqueous solution is dropwise added, the hydrogen peroxide aqueous solution is used as an oxidant, the mass fraction of the hydrogen peroxide aqueous solution is controlled to be 30%, active oxygen ions are generated in the solution under the concentration, the salicylaldehyde can be oxidized, a material A is prepared, the material A is an oligomeric salicylaldehyde precursor, in the step S3, a material B is prepared through urea and ammonium phosphate, the material B is a flame retardant, in the prior art, the nano particle filler and the flame retardant are directly compounded with PET, the PET is endowed with flame retardant performance, but the nano particle filler cannot be uniformly dispersed in the PET and the problem that the flame retardant is wet cannot be solved, so that the nano particle filler, the material A and the material B are mixed according to the weight ratio of 1: 0.05-0.08 in the step S3 of the invention, and then are melted and mixed with the PET to form the filler integrating the carbon source, the acid source and the air source, thereby not only solving the problem that the nano particle filler is not easy to disperse, but also endowing the PET with excellent flame retardant performance.
Further, the weight ratio of glucose and deionized water is controlled to be 1: 10-12 in step S1, and the amount ratio of salicylaldehyde, sodium hydroxide and hydrogen peroxide is controlled to be 1: 0.5: 1 in step S2.
Further, the toughening filler is prepared by the following method:
step S11, adding polyacrylonitrile into a sodium carbonate solution with the mass fraction of 10%, heating in a water bath at 35-45 ℃ and magnetically stirring for 20-30min to obtain primarily treated polyacrylonitrile, then adding sodium hydrosulfite, heating to 60-65 ℃, continuously stirring for 30min, taking out, grinding and filtering to obtain polyacrylonitrile powder;
and S12, adding the polyacrylonitrile powder and the graphene powder prepared in the step S11 into N, N-dimethylformamide, performing ultrasonic treatment for 10-12h at 35-45 ℃, then adding the mixture into polyvinyl alcohol spinning solution, spinning, performing dry heat stretching for 2-4.5 times at the temperature of 150-180 ℃, then performing acetalization treatment to prepare the composite fiber filler, and then crushing and grinding to prepare the toughening filler.
In the step S11, polyacrylonitrile is firstly subjected to primary treatment through a 10% sodium carbonate solution and sodium hydrosulfite, then polyacrylonitrile powder and graphene powder are mixed in N, N-dimethylformamide in the step S12, the mixture is added into a polyvinyl alcohol spinning solution for spinning to prepare a composite fiber filler, the composite fiber filler takes a polyvinyl alcohol core layer and polyacrylonitrile as a surface layer, and then the composite fiber filler is crushed and ground to prepare a toughening filler, wherein the toughening filler has excellent mechanical properties, the stability of a system can be guaranteed, and the finally prepared master batch has excellent toughness.
Further, the weight ratio of polyacrylonitrile, 10% sodium carbonate solution and sodium hydrosulfite is controlled to be 1: 35-40: 0.5-1 in step S11, and the weight ratio of polyacrylonitrile powder, graphene powder and polyvinyl alcohol spinning solution is controlled to be 5: 2: 15 in step S12.
A preparation method of a high flame retardant color master batch comprises the following steps:
firstly, sequentially adding flame-retardant PET, toner, toughening filler, dispersant, magnesium silicate, vitamin E and lignocellulose into a high-speed stirring kettle, and stirring at the rotating speed of 480-;
and secondly, adding the mixture prepared in the first step into a double-screw extruder for blending, controlling the blending temperature to be 200-250 ℃, controlling the screw rotating speed to be 200r/min, transferring the mixture into an internal mixer for internal mixing after the mixing is finished, controlling the internal mixing temperature to be 350-400 ℃, and controlling the internal mixing time to be 20-30min, and then carrying out bracing and granulating treatment to prepare the high-flame-retardancy color master batch.
The invention has the beneficial effects that:
(1) the invention relates to a high-flame-retardancy color master batch which is prepared by taking flame-retardant PET, toughening filler and the like as raw materials, wherein the flame-retardant PET is prepared into a glucose solution in a step S1 in the preparation process, and then is subjected to heat preservation at the temperature of 280 plus one material for 8 hours at 300 ℃ to prepare a nano particle filler, the nano particle filler is a carbon material, the surface of the nano particle filler contains a large amount of hydroxyl and carboxyl, so the nano particle filler has large specific surface area, small density and excellent thermal stability, in the step S2, salicylaldehyde is added into a sodium hydroxide aqueous solution, then a hydrogen peroxide aqueous solution is dropwise added, the hydrogen peroxide aqueous solution is taken as an oxidant, the mass fraction of the hydrogen peroxide aqueous solution is controlled to be 30 percent, active oxygen ions are generated in the solution at the concentration, the salicylaldehyde can be oxidized to prepare a material A, the material A is an oligomeric salicylaldehyde precursor, in the step S3, a material B is prepared by, the material B is a flame retardant, and the nano particle filler, the flame retardant and the PET are directly compounded in the prior art to endow the PET with flame retardant performance, but the nano particle filler cannot be uniformly dispersed in the PET and the problem that the flame retardant is wet cannot be solved, so that the nano particle filler, the material A and the material B are mixed according to the weight ratio of 1: 0.05-0.08 in the step S3 and then are melted and mixed with the PET to form the filler integrating a carbon source, an acid source and an air source, so that the problem that the nano particle filler is not easy to disperse is solved, the PET can be endowed with excellent flame retardant performance, and the master batch is endowed with excellent flame retardant performance;
(2) in the preparation process of the toughening filler, in step S11, polyacrylonitrile is firstly subjected to primary treatment through a 10% sodium carbonate solution and sodium hydrosulfite, then in step S12, polyacrylonitrile powder and graphene powder are mixed in N, N-dimethylformamide and added into polyvinyl alcohol spinning solution for spinning to prepare the composite fiber filler, the composite fiber filler takes a polyvinyl alcohol core layer and polyacrylonitrile as a surface layer, and then the polyvinyl alcohol core layer and the graphene powder are crushed and ground to prepare the toughening filler, the toughening filler has excellent mechanical properties, the stability of a system can be guaranteed, and the finally prepared master batch is endowed with excellent toughness.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The high-flame-retardancy color master batch comprises the following raw materials in parts by weight: 30 parts of flame-retardant PET, 10 parts of phthalocyanine red, 15 parts of toughening filler, 1 part of polyethylene glycol, 1 part of magnesium silicate, 2 parts of vitamin E and 6 parts of lignocellulose;
the high-flame-retardancy color master batch is prepared by the following method:
firstly, sequentially adding flame-retardant PET, phthalocyanine red, toughening filler, polyethylene glycol, magnesium silicate, vitamin E and lignocellulose into a high-speed stirring kettle, and stirring at the rotating speed of 480r/min for 10min to prepare a mixture;
and secondly, adding the mixture prepared in the first step into a double-screw extruder for blending, controlling the blending temperature to be 200 ℃ and the screw rotating speed to be 200r/min, transferring the mixture into an internal mixer for internal mixing after the mixing is finished, controlling the internal mixing temperature to be 350 ℃ and the internal mixing time to be 20min, and then carrying out bracing and granulating treatment to obtain the high-flame-retardancy color master batch.
The flame-retardant PET is prepared by the following method:
step S1, adding glucose into deionized water, heating in a water bath at 35 ℃, stirring at a rotating speed of 100r/min for 30min to prepare a glucose solution, transferring the glucose solution into a high-pressure reaction kettle, heating to 280 ℃ at a speed of 5 ℃/min, preserving heat at the temperature for 8h, cooling and filtering after heat preservation, washing a filter cake with absolute ethyl alcohol and deionized water for three times respectively, and transferring to a drying box at 80 ℃ for drying for 12h to prepare a nano particle filler, wherein the weight ratio of the glucose to the deionized water is controlled to be 1: 10;
step S2, adding salicylaldehyde into a 10 mass percent sodium hydroxide aqueous solution, uniformly stirring for 15min, transferring to a three-neck flask, heating in a water bath at 35 ℃, magnetically stirring for 20min, then dropwise adding a 30 mass percent hydrogen peroxide aqueous solution, controlling the dropwise adding time to be 30min, then heating to 45 ℃, continuing stirring for 10min, centrifuging, filtering, transferring to an oven at 85 ℃ for drying for 4h, and preparing a material A, wherein the mass ratio of salicylaldehyde to sodium hydroxide to hydrogen peroxide is controlled to be 1: 0.5: 1;
step S3, adding urea and ammonium phosphate into a three-neck flask according to the molar ratio of 1: 1.5, heating in water bath at 100 ℃, stirring for 15min at the rotating speed of 180r/min, adding the mixture into an evaporation pan, transferring the mixture into a drying oven at 200 ℃, drying for 2h, cooling, washing with absolute ethyl alcohol and deionized water for three times respectively, and drying to obtain a material B;
step S4, mixing the prepared nano particle filler, the material A and the material B according to the weight ratio of 1: 0.05 to prepare the filler, slicing PET, drying at 80 ℃ for 10h, adding the PET and the filler into a double-screw extruder, carrying out melt extrusion and grain cutting, transferring the PET and the filler into a vulcanizing machine, and pressing at the pressure of 20MPa and the temperature of 150 ℃ for 15min to prepare the flame-retardant PET, wherein the weight ratio of the filler to the PET is controlled to be 0.1: 1.
The toughening filler is prepared by the following method:
step S11, adding polyacrylonitrile into a sodium carbonate solution with the mass fraction of 10%, heating in a water bath at 35 ℃ and magnetically stirring for 20min to obtain polyacrylonitrile after primary treatment, then adding sodium hydrosulfite, heating to 60 ℃, continuing stirring for 30min, taking out, grinding and filtering to obtain polyacrylonitrile powder, wherein the weight ratio of the polyacrylonitrile to the sodium carbonate solution with the mass fraction of 10% to the sodium hydrosulfite is controlled to be 1: 35: 0.5;
and S12, adding the polyacrylonitrile powder and the graphene powder prepared in the step S11 into N, N-dimethylformamide, performing ultrasonic treatment for 10 hours at 35 ℃, then adding the mixture into polyvinyl alcohol spinning solution, spinning, performing dry heat stretching for 2 times at 150 ℃, performing acetalization treatment to obtain a composite fiber filler, then crushing and grinding to obtain the toughening filler, and controlling the weight ratio of the polyacrylonitrile powder, the graphene powder and the polyvinyl alcohol spinning solution to be 5: 2: 15.
Example 2
The high-flame-retardancy color master batch comprises the following raw materials in parts by weight: 35 parts of flame-retardant PET, 14 parts of phthalocyanine red, 18 parts of toughening filler, 3 parts of polyethylene glycol, 2 parts of magnesium silicate, 3 parts of vitamin E and 7 parts of lignocellulose;
the high-flame-retardancy color master batch is prepared by the following method:
firstly, sequentially adding flame-retardant PET, phthalocyanine red, toughening filler, polyethylene glycol, magnesium silicate, vitamin E and lignocellulose into a high-speed stirring kettle, and stirring at the rotating speed of 480r/min for 10min to prepare a mixture;
and secondly, adding the mixture prepared in the first step into a double-screw extruder for blending, controlling the blending temperature to be 200 ℃ and the screw rotating speed to be 200r/min, transferring the mixture into an internal mixer for internal mixing after the mixing is finished, controlling the internal mixing temperature to be 350 ℃ and the internal mixing time to be 20min, and then carrying out bracing and granulating treatment to obtain the high-flame-retardancy color master batch.
The flame-retardant PET is prepared by the following method:
step S1, adding glucose into deionized water, heating in a water bath at 35 ℃, stirring at a rotating speed of 100r/min for 30min to prepare a glucose solution, transferring the glucose solution into a high-pressure reaction kettle, heating to 280 ℃ at a speed of 5 ℃/min, preserving heat at the temperature for 8h, cooling and filtering after heat preservation, washing a filter cake with absolute ethyl alcohol and deionized water for three times respectively, and transferring to a drying box at 80 ℃ for drying for 12h to prepare a nano particle filler, wherein the weight ratio of the glucose to the deionized water is controlled to be 1: 10;
step S2, adding salicylaldehyde into a 10 mass percent sodium hydroxide aqueous solution, uniformly stirring for 15min, transferring to a three-neck flask, heating in a water bath at 35 ℃, magnetically stirring for 20min, then dropwise adding a 30 mass percent hydrogen peroxide aqueous solution, controlling the dropwise adding time to be 30min, then heating to 45 ℃, continuing stirring for 10min, centrifuging, filtering, transferring to an oven at 85 ℃ for drying for 4h, and preparing a material A, wherein the mass ratio of salicylaldehyde to sodium hydroxide to hydrogen peroxide is controlled to be 1: 0.5: 1;
step S3, adding urea and ammonium phosphate into a three-neck flask according to the molar ratio of 1: 1.5, heating in water bath at 100 ℃, stirring for 15min at the rotating speed of 180r/min, adding the mixture into an evaporation pan, transferring the mixture into a drying oven at 200 ℃, drying for 2h, cooling, washing with absolute ethyl alcohol and deionized water for three times respectively, and drying to obtain a material B;
step S4, mixing the prepared nano particle filler, the material A and the material B according to the weight ratio of 1: 0.05 to prepare the filler, slicing PET, drying at 80 ℃ for 10h, adding the PET and the filler into a double-screw extruder, carrying out melt extrusion and grain cutting, transferring the PET and the filler into a vulcanizing machine, and pressing at the pressure of 20MPa and the temperature of 150 ℃ for 15min to prepare the flame-retardant PET, wherein the weight ratio of the filler to the PET is controlled to be 0.1: 1.
The toughening filler is prepared by the following method:
step S11, adding polyacrylonitrile into a sodium carbonate solution with the mass fraction of 10%, heating in a water bath at 35 ℃ and magnetically stirring for 20min to obtain polyacrylonitrile after primary treatment, then adding sodium hydrosulfite, heating to 60 ℃, continuing stirring for 30min, taking out, grinding and filtering to obtain polyacrylonitrile powder, wherein the weight ratio of the polyacrylonitrile to the sodium carbonate solution with the mass fraction of 10% to the sodium hydrosulfite is controlled to be 1: 35: 0.5;
and S12, adding the polyacrylonitrile powder and the graphene powder prepared in the step S11 into N, N-dimethylformamide, performing ultrasonic treatment for 10 hours at 35 ℃, then adding the mixture into polyvinyl alcohol spinning solution, spinning, performing dry heat stretching for 2 times at 150 ℃, performing acetalization treatment to obtain a composite fiber filler, then crushing and grinding to obtain the toughening filler, and controlling the weight ratio of the polyacrylonitrile powder, the graphene powder and the polyvinyl alcohol spinning solution to be 5: 2: 15.
Example 3
The high-flame-retardancy color master batch comprises the following raw materials in parts by weight: 45 parts of flame-retardant PET, 16 parts of phthalocyanine red, 22 parts of toughening filler, 4 parts of polyethylene glycol, 2 parts of magnesium silicate, 4 parts of vitamin E and 7 parts of lignocellulose;
the high-flame-retardancy color master batch is prepared by the following method:
firstly, sequentially adding flame-retardant PET, phthalocyanine red, toughening filler, polyethylene glycol, magnesium silicate, vitamin E and lignocellulose into a high-speed stirring kettle, and stirring at the rotating speed of 480r/min for 10min to prepare a mixture;
and secondly, adding the mixture prepared in the first step into a double-screw extruder for blending, controlling the blending temperature to be 200 ℃ and the screw rotating speed to be 200r/min, transferring the mixture into an internal mixer for internal mixing after the mixing is finished, controlling the internal mixing temperature to be 350 ℃ and the internal mixing time to be 20min, and then carrying out bracing and granulating treatment to obtain the high-flame-retardancy color master batch.
The flame-retardant PET is prepared by the following method:
step S1, adding glucose into deionized water, heating in a water bath at 35 ℃, stirring at a rotating speed of 100r/min for 30min to prepare a glucose solution, transferring the glucose solution into a high-pressure reaction kettle, heating to 280 ℃ at a speed of 5 ℃/min, preserving heat at the temperature for 8h, cooling and filtering after heat preservation, washing a filter cake with absolute ethyl alcohol and deionized water for three times respectively, and transferring to a drying box at 80 ℃ for drying for 12h to prepare a nano particle filler, wherein the weight ratio of the glucose to the deionized water is controlled to be 1: 10;
step S2, adding salicylaldehyde into a 10 mass percent sodium hydroxide aqueous solution, uniformly stirring for 15min, transferring to a three-neck flask, heating in a water bath at 35 ℃, magnetically stirring for 20min, then dropwise adding a 30 mass percent hydrogen peroxide aqueous solution, controlling the dropwise adding time to be 30min, then heating to 45 ℃, continuing stirring for 10min, centrifuging, filtering, transferring to an oven at 85 ℃ for drying for 4h, and preparing a material A, wherein the mass ratio of salicylaldehyde to sodium hydroxide to hydrogen peroxide is controlled to be 1: 0.5: 1;
step S3, adding urea and ammonium phosphate into a three-neck flask according to the molar ratio of 1: 1.5, heating in water bath at 100 ℃, stirring for 15min at the rotating speed of 180r/min, adding the mixture into an evaporation pan, transferring the mixture into a drying oven at 200 ℃, drying for 2h, cooling, washing with absolute ethyl alcohol and deionized water for three times respectively, and drying to obtain a material B;
step S4, mixing the prepared nano particle filler, the material A and the material B according to the weight ratio of 1: 0.05 to prepare the filler, slicing PET, drying at 80 ℃ for 10h, adding the PET and the filler into a double-screw extruder, carrying out melt extrusion and grain cutting, transferring the PET and the filler into a vulcanizing machine, and pressing at the pressure of 20MPa and the temperature of 150 ℃ for 15min to prepare the flame-retardant PET, wherein the weight ratio of the filler to the PET is controlled to be 0.1: 1.
The toughening filler is prepared by the following method:
step S11, adding polyacrylonitrile into a sodium carbonate solution with the mass fraction of 10%, heating in a water bath at 35 ℃ and magnetically stirring for 20min to obtain polyacrylonitrile after primary treatment, then adding sodium hydrosulfite, heating to 60 ℃, continuing stirring for 30min, taking out, grinding and filtering to obtain polyacrylonitrile powder, wherein the weight ratio of the polyacrylonitrile to the sodium carbonate solution with the mass fraction of 10% to the sodium hydrosulfite is controlled to be 1: 35: 0.5;
and S12, adding the polyacrylonitrile powder and the graphene powder prepared in the step S11 into N, N-dimethylformamide, performing ultrasonic treatment for 10 hours at 35 ℃, then adding the mixture into polyvinyl alcohol spinning solution, spinning, performing dry heat stretching for 2 times at 150 ℃, performing acetalization treatment to obtain a composite fiber filler, then crushing and grinding to obtain the toughening filler, and controlling the weight ratio of the polyacrylonitrile powder, the graphene powder and the polyvinyl alcohol spinning solution to be 5: 2: 15.
Example 4
The high-flame-retardancy color master batch comprises the following raw materials in parts by weight: 50 parts of flame-retardant PET, 20 parts of phthalocyanine red, 25 parts of toughening filler, 5 parts of polyethylene glycol, 3 parts of magnesium silicate, 5 parts of vitamin E and 8 parts of lignocellulose;
the high-flame-retardancy color master batch is prepared by the following method:
firstly, sequentially adding flame-retardant PET, phthalocyanine red, toughening filler, polyethylene glycol, magnesium silicate, vitamin E and lignocellulose into a high-speed stirring kettle, and stirring at the rotating speed of 480r/min for 10min to prepare a mixture;
and secondly, adding the mixture prepared in the first step into a double-screw extruder for blending, controlling the blending temperature to be 200 ℃ and the screw rotating speed to be 200r/min, transferring the mixture into an internal mixer for internal mixing after the mixing is finished, controlling the internal mixing temperature to be 350 ℃ and the internal mixing time to be 20min, and then carrying out bracing and granulating treatment to obtain the high-flame-retardancy color master batch.
The flame-retardant PET is prepared by the following method:
step S1, adding glucose into deionized water, heating in a water bath at 35 ℃, stirring at a rotating speed of 100r/min for 30min to prepare a glucose solution, transferring the glucose solution into a high-pressure reaction kettle, heating to 280 ℃ at a speed of 5 ℃/min, preserving heat at the temperature for 8h, cooling and filtering after heat preservation, washing a filter cake with absolute ethyl alcohol and deionized water for three times respectively, and transferring to a drying box at 80 ℃ for drying for 12h to prepare a nano particle filler, wherein the weight ratio of the glucose to the deionized water is controlled to be 1: 10;
step S2, adding salicylaldehyde into a 10 mass percent sodium hydroxide aqueous solution, uniformly stirring for 15min, transferring to a three-neck flask, heating in a water bath at 35 ℃, magnetically stirring for 20min, then dropwise adding a 30 mass percent hydrogen peroxide aqueous solution, controlling the dropwise adding time to be 30min, then heating to 45 ℃, continuing stirring for 10min, centrifuging, filtering, transferring to an oven at 85 ℃ for drying for 4h, and preparing a material A, wherein the mass ratio of salicylaldehyde to sodium hydroxide to hydrogen peroxide is controlled to be 1: 0.5: 1;
step S3, adding urea and ammonium phosphate into a three-neck flask according to the molar ratio of 1: 1.5, heating in water bath at 100 ℃, stirring for 15min at the rotating speed of 180r/min, adding the mixture into an evaporation pan, transferring the mixture into a drying oven at 200 ℃, drying for 2h, cooling, washing with absolute ethyl alcohol and deionized water for three times respectively, and drying to obtain a material B;
step S4, mixing the prepared nano particle filler, the material A and the material B according to the weight ratio of 1: 0.05 to prepare the filler, slicing PET, drying at 80 ℃ for 10h, adding the PET and the filler into a double-screw extruder, carrying out melt extrusion and grain cutting, transferring the PET and the filler into a vulcanizing machine, and pressing at the pressure of 20MPa and the temperature of 150 ℃ for 15min to prepare the flame-retardant PET, wherein the weight ratio of the filler to the PET is controlled to be 0.1: 1.
The toughening filler is prepared by the following method:
step S11, adding polyacrylonitrile into a sodium carbonate solution with the mass fraction of 10%, heating in a water bath at 35 ℃ and magnetically stirring for 20min to obtain polyacrylonitrile after primary treatment, then adding sodium hydrosulfite, heating to 60 ℃, continuing stirring for 30min, taking out, grinding and filtering to obtain polyacrylonitrile powder, wherein the weight ratio of the polyacrylonitrile to the sodium carbonate solution with the mass fraction of 10% to the sodium hydrosulfite is controlled to be 1: 35: 0.5;
and S12, adding the polyacrylonitrile powder and the graphene powder prepared in the step S11 into N, N-dimethylformamide, performing ultrasonic treatment for 10 hours at 35 ℃, then adding the mixture into polyvinyl alcohol spinning solution, spinning, performing dry heat stretching for 2 times at 150 ℃, performing acetalization treatment to obtain a composite fiber filler, then crushing and grinding to obtain the toughening filler, and controlling the weight ratio of the polyacrylonitrile powder, the graphene powder and the polyvinyl alcohol spinning solution to be 5: 2: 15.
Comparative example 1
This comparative example compares to example 1 with PET instead of flame retardant PET.
Comparative example 2
In comparison to example 1, no toughening filler was added in this comparative example.
Comparative example 3
The comparative example is a flame retardant color master batch in the market.
The flame retardant properties, impact strength and tensile strength of examples 1 to 4 and comparative examples 1 to 3 were measured, and the results are shown in the following table;
| flame retardant rating | Impact Strength/J.m-1 | Tensile strength MPa | |
| Example 1 | V0 | 25.3 | 36.8 |
| Example 2 | V0 | 25.5 | 37.0 |
| Example 3 | V0 | 25.3 | 36.5 |
| Example 4 | V0 | 25.2 | 36.8 |
| Comparative example 1 | V2 | 23.1 | 34.2 |
| Comparative example 2 | V1 | 21.2 | 31.5 |
| Comparative example 3 | V1 | 20.8 | 30.2 |
From the above table, it can be seen that examples 1 to 4 had a flame retardancy rating of V0 and an impact strength of 25.2 to 25.3 J.m-1Tensile strength of 36.5-37.0MPa, flame retardant rating of V2-V1 for comparative examples 1-3, and impact strength of 20.8-23.1 J.m-1The tensile strength is 30.2-34.2 MPa; therefore, in step S3, the nano particle filler, the material A and the material B are mixed according to the weight ratio of 1: 0.05-0.08, and then are melted and mixed with the PET to form the filler integrating the carbon source, the acid source and the air source, so that the problem that the nano particle filler is not easy to disperse is solved, the PET can be endowed with excellent flame retardant property, and the master batch is endowed with excellent flame retardant property.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (7)
1. The high-flame-retardancy color master batch is characterized by comprising the following raw materials in parts by weight: 30-50 parts of flame-retardant PET, 10-20 parts of toner, 15-25 parts of toughening filler, 1-5 parts of dispersant, 1-3 parts of magnesium silicate, 2-5 parts of vitamin E and 6-8 parts of lignocellulose;
the high-flame-retardancy color master batch is prepared by the following method:
firstly, sequentially adding flame-retardant PET, toner, toughening filler, dispersant, magnesium silicate, vitamin E and lignocellulose into a high-speed stirring kettle, and stirring at the rotating speed of 480-;
and secondly, adding the mixture prepared in the first step into a double-screw extruder for blending, controlling the blending temperature to be 200-250 ℃, controlling the screw rotating speed to be 200r/min, transferring the mixture into an internal mixer for internal mixing after the mixing is finished, controlling the internal mixing temperature to be 350-400 ℃, and controlling the internal mixing time to be 20-30min, and then carrying out bracing and granulating treatment to prepare the high-flame-retardancy color master batch.
2. The color master batch with high flame retardance according to claim 1, wherein the toner is any one of phthalocyanine red, phthalocyanine blue and phthalocyanine green, and the dispersant is one or two of stearic acid monoglyceride and polyethylene glycol mixed in any proportion.
3. The color master batch with high flame retardancy according to claim 1, wherein the flame retardant PET is prepared by the following method:
step S1, adding glucose into deionized water, heating in a water bath at 35-40 ℃, stirring for 30min at a rotating speed of 120r/min for 100 plus materials to obtain a glucose solution, transferring the glucose solution into a high-pressure reaction kettle, heating to 300 ℃ at a speed of 5-8 ℃/min, preserving heat for 8h at the temperature, cooling and filtering after finishing preserving heat, washing a filter cake three times by using absolute ethyl alcohol and deionized water respectively, and transferring into a drying box at 80-90 ℃ for drying for 12h to obtain a nanoparticle filler;
step S2, adding salicylaldehyde into a sodium hydroxide aqueous solution with the mass fraction of 10%, uniformly stirring for 15min, transferring to a three-neck flask, heating in a water bath at 35-40 ℃, magnetically stirring for 20min, then dropwise adding a hydrogen peroxide aqueous solution with the mass fraction of 30%, controlling the dropwise adding time to be 30-45min, then heating to 45-50 ℃, continuing stirring for 10min, centrifuging, filtering, transferring to an oven with the temperature of 85-90 ℃ and drying for 4-5h to obtain a material A;
step S3, adding urea and ammonium phosphate into a three-neck flask according to the molar ratio of 1: 1.5-1.8, heating in a water bath at 110 ℃ under 100-;
step S4, mixing the prepared nano particle filler, the material A and the material B according to the weight ratio of 1: 0.05-0.08 to prepare the filler, slicing the PET, drying at 80 ℃ for 10 hours, adding the PET and the filler into a double-screw extruder, melting, extruding and granulating, transferring into a vulcanizing machine, and pressing at the pressure of 20MPa and the temperature of 150 ℃ for 15min to prepare the flame-retardant PET, wherein the weight ratio of the filler to the PET is controlled to be 0.1-0.3: 1.
4. The color masterbatch with high flame retardancy of claim 3, wherein the weight ratio of glucose and deionized water is controlled to 1: 10-12 in step S1, and the amount ratio of salicylaldehyde, sodium hydroxide and hydrogen peroxide is controlled to 1: 0.5: 1 in step S2.
5. The color masterbatch with high flame retardancy according to claim 1, wherein the toughening filler is prepared by the following steps:
step S11, adding polyacrylonitrile into a sodium carbonate solution with the mass fraction of 10%, heating in a water bath at 35-45 ℃ and magnetically stirring for 20-30min to obtain primarily treated polyacrylonitrile, then adding sodium hydrosulfite, heating to 60-65 ℃, continuously stirring for 30min, taking out, grinding and filtering to obtain polyacrylonitrile powder;
and S12, adding the polyacrylonitrile powder and the graphene powder prepared in the step S11 into N, N-dimethylformamide, performing ultrasonic treatment for 10-12h at 35-45 ℃, then adding the mixture into polyvinyl alcohol spinning solution, spinning, performing dry heat stretching for 2-4.5 times at the temperature of 150-180 ℃, then performing acetalization treatment to prepare the composite fiber filler, and then crushing and grinding to prepare the toughening filler.
6. The color masterbatch with high flame retardancy according to claim 5, wherein the weight ratio of polyacrylonitrile, 10% sodium carbonate solution and sodium dithionite in step S11 is controlled to be 1: 35-40: 0.5-1, and the weight ratio of polyacrylonitrile powder, graphene powder and polyvinyl alcohol spinning solution in step S12 is controlled to be 5: 2: 15.
7. The preparation method of the color master batch with high flame retardance according to claim 1, characterized by comprising the following steps:
firstly, sequentially adding flame-retardant PET, toner, toughening filler, dispersant, magnesium silicate, vitamin E and lignocellulose into a high-speed stirring kettle, and stirring at the rotating speed of 480-;
and secondly, adding the mixture prepared in the first step into a double-screw extruder for blending, controlling the blending temperature to be 200-250 ℃, controlling the screw rotating speed to be 200r/min, transferring the mixture into an internal mixer for internal mixing after the mixing is finished, controlling the internal mixing temperature to be 350-400 ℃, and controlling the internal mixing time to be 20-30min, and then carrying out bracing and granulating treatment to prepare the high-flame-retardancy color master batch.
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