Flame-retardant fireproof plastic and preparation method thereof

By aminating and ultrasonic blending of sepiolite, combined with the modified filler and melt blending with polycarbonate, polycarbonate plastics with high flame retardant properties were prepared, which solved the insufficient flame retardant properties of polycarbonate plastics. Problem, significant flame retardant and fire-retardant effects have been achieved.

CN119264633AInactive Publication Date: 2025-01-07QINGDAO DONGYIYUE NEW MATERIAL CO LTD

Patent Information

Application Number
CN202411563139.7
Authority / Receiving Office
CN · China
Patent Type
Applications(China)
Current Assignee / Owner
Filing Date
2024-11-05
Publication Date
2025-01-07
Estimated Expiration
Not applicable · inactive patent

AI Technical Summary

Technical Problem

Polycarbonate plastics have insufficient flame retardant properties. Existing flame retardants such as bromine and sulfonate systems have problems with flue gas toxicity and environmental toxicity. Phosphorus and silicon-based flame retardants have low flame retardant efficiency and are not as good as polycarbonate. Compatible and cannot meet the high flame retardant requirements.

Method used

Sepiolite is used as raw material, and it is amino-aminopropyltriethoxysilane treatment is treated and ultrasonic blended with modified filler and phytic acid to form flame retardant filler, and then with bisphenol A polycarbonate The ester is melt blended to produce flame retardant and fire-resistant plastic with modified fillers. This method improves the flame retardant properties of the material through grafting reaction and sonication.

Benefits of technology

During combustion, the flame retardant filler forms an isolation layer. The evaporation of water molecules takes away heat, and the produced inorganic acid and phosphate esters are dehydrated and carbonized. Combined with the silicone structure and aluminum and magnesium ion oxides, it significantly improves the flame retardant and fire-retardant effect of plastics. .

✦ Generated by Eureka AI based on patent content.
Patent Text Reader

Abstract

The preparation method comprises the following steps: treating sepiolite serving as a raw material with 3-aminopropyltriethoxysilane to prepare aminated sepiolite, ultrasonically blending the aminated sepiolite and a modified filler, then treating with phytic acid to prepare a flame-retardant filler, melting bisphenol A polycarbonate, blending with the flame-retardant filler, and carrying out extrusion molding to obtain the flame-retardant fireproof plastic. When the flame-retardant fireproof plastic is combusted, the flame-retardant filler is subjected to evaporation of hot water molecules to cause structural expansion and form an isolation layer, meanwhile, evaporation of the water molecules can take away heat, released ammonia gas can reduce the content of smoke so as to achieve the flame-retardant effect, and generated inorganic acid and phosphate ester are dehydrated and carbonized, so that the flame-retardant fireproof plastic has a good flame-retardant effect. The carbon layer with large interlayer spacing is formed through cooperation with the isolation layer, an organic silicon structure is contained, Si-C can be formed, then the density of the carbon layer is increased, aluminum oxide and magnesium oxide can be formed after internal aluminum ions and magnesium ions are combusted at high temperature, then the flame retardance of the carbon layer is improved, and the flame-retardant and fireproof effects of the plastic are improved.
Need to check novelty before this filing date? Find Prior Art

Description

Technical Field

[0001] The invention relates to the technical field of flame retardant plastic preparation, and in particular to a flame retardant and fireproof plastic and a preparation method thereof. Background Art

[0002] Polycarbonate is a high-performance thermoplastic engineering plastic that is widely used in various fields for its excellent transparency, impact resistance and heat resistance. However, the UL-94 vertical combustion rating of PC is V-2, and the LOI is only 25.0%. Its flame retardant performance cannot meet the requirements in application scenarios with high flame retardancy requirements. Adding flame retardants to PC is the most direct and effective way to improve its flame retardant properties. However, due to the smoke toxicity and environmental toxicity of bromine-based and sulfonate-based flame retardants, these two types of high-efficiency flame retardants for PC are gradually banned. The phosphorus-based and silicon-based flame retardants currently used in PC face problems such as low flame retardant efficiency, large addition amount and poor compatibility with PC, and cannot meet the flame retardant requirements of polycarbonate. Summary of the invention

[0003] The purpose of the present invention is to provide a flame retardant and fireproof plastic and a preparation method thereof, so as to solve the problem that the flame retardant and fireproof effect of polycarbonate plastic is poor at present.

[0004] The purpose of the present invention can be achieved through the following technical solutions: A method for preparing a flame retardant and fireproof plastic comprises the following steps: Step A1: Disperse sepiolite in ethanol, stir and add 3-aminopropyltriethoxysilane and deionized water at a speed of 200-300 r / min and a temperature of 60-70° C., and react for 2-3 hours to obtain amination sepiolite; Step A2: uniformly mix the aminated sepiolite, the modified filler and deionized water, perform ultrasound at a frequency of 20-30 kHz and a temperature of 80-85° C., add phytic acid, raise the temperature to 90-95° C., and react for 5-7 hours to obtain a flame retardant filler; Step A3: Add bisphenol A polycarbonate into an internal mixer, melt it at a speed of 60-80 r / min and a temperature of 240-250° C., add flame retardant filler, melt blend for 8-10 minutes, hot press and cool to obtain flame retardant and fireproof plastic.

[0005] Furthermore, the amount of 3-aminopropyltriethoxysilane used in step A1 is 3% of the mass of sepiolite.

[0006] Furthermore, the usage ratio of the amination sepiolite, modified filler and phytic acid described in step A2 is 3g0:5g:10mL.

[0007] Furthermore, the mass ratio of the bisphenol A polycarbonate and the flame retardant filler in step A3 is 100:10-15, and the model of the bisphenol A polycarbonate is 25037-45-0.

[0008] Further, the modified filler is prepared by the following steps: Step B1: octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, tetramethylammonium hydroxide, 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane and dimethyl sulfoxide are uniformly mixed, nitrogen is introduced for protection, and the reaction is carried out for 3-5 hours at a speed of 120-150 r / min and a temperature of 105-110° C. to obtain a diamine-terminated polysiloxane; ammonium polyphosphate, terephthalaldehyde and DMF are uniformly mixed, and the diamine-terminated polysiloxane is added under stirring at a speed of 150-200 r / min and a temperature of 65-70° C., and the reaction is carried out for 8-10 hours to obtain a pretreated ammonium polyphosphate; Step B2: dissolving DOPO in ethanol, introducing nitrogen protection, stirring and adding azobisisobutyronitrile and pretreated ammonium polyphosphate at a speed of 120-150 r / min and a temperature of 65-70° C., reacting for 20-25 hours to obtain modified ammonium polyphosphate, and uniformly mixing the modified ammonium polyphosphate, methacryloyloxypropylmethyldichlorosilane, chloroplatinic acid and DMF, introducing nitrogen protection, and reacting for 4-6 hours at a speed of 60-80 r / min and a temperature of 75-80° C. to obtain functionalized ammonium polyphosphate; Step B3: 3-aminopropyltriethoxysilane, tert-butyloxycarbonyl chloride and DMF are mixed uniformly, and triethylamine is added under the conditions of a rotation speed of 120-150 r / min and a temperature of 30-40° C., and the mixture is stirred and reacted for 4-6 hours to obtain a modified monomer, and the modified monomer, isopropanol, deionized water and sodium hydroxide are mixed, and the mixture is reacted for 3-5 hours under the conditions of a rotation speed of 60-80 r / min and a temperature of 85-90° C., and then the mixture is cooled to 20-25° C. and reacted for 14-16 hours to obtain a modifier; Step B4: Evenly mix the modifier, triethylamine and tetrahydrofuran, introduce nitrogen protection, stir and add functionalized ammonium polyphosphate at a speed of 120-150r / min and a temperature of 0°C, react for 3-5h, heat to 20-25°C, react for 20-25h to obtain a precursor, disperse the precursor in tetrahydrofuran, stir and add zinc bromide at a speed of 120-150r / min and a temperature of 10-15°C, stir for 3-5h to obtain a modified filler.

[0009] Furthermore, the molar ratio of octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, tetramethylammonium hydroxide and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane described in step B1 is 1.4:1:3:2, and the molar ratio of ammonium polyphosphate, terephthalaldehyde and diamine-terminated polysiloxane is 4 g:5 mmol:5 mmol.

[0010] Furthermore, the molar ratio of the C=N bond on the pretreated ammonium polyphosphate described in step B2 to DOPO is 1:1, the amount of azobisisobutyronitrile is 1‰ of the mass of DOPO, the molar ratio of the Si-H bond on the modified ammonium polyphosphate to methacryloxypropylmethyldichlorosilane is 1:1, and the amount of chloroplatinic acid is 1‰ of the mass of methacryloxypropylmethyldichlorosilane.

[0011] Furthermore, the molar ratio of 3-aminopropyltriethoxysilane, tert-butyloxycarbonyl chloride and triethylamine in step B3 is 1:1:1, and the amount ratio of modified monomer, isopropanol, deionized water and sodium hydroxide is 120mmol:120mL:3mL:80mmol.

[0012] Furthermore, the amount ratio of the modifier, triethylamine, tetrahydrofuran and functionalized ammonium polyphosphate described in step B4 is 8g:5mL:30mL:3g, and the amount ratio of the precursor, tetrahydrofuran and zinc bromide is 3g:20mL:1g.

[0013] Beneficial effects of the present invention: a flame retardant and fireproof plastic prepared by the present invention is prepared by using sepiolite as a raw material and treating it with 3-aminopropyltriethoxysilane so that amino groups are grafted on the surface of the sepiolite to prepare amino sepiolite, and the amino sepiolite and the modified filler are ultrasonically blended, and then treated with phytic acid so that the phosphoric acid groups on the phytic acid and the amino groups on the amino sepiolite and the modified filler are grafted to prepare the flame retardant filler, and bisphenol A type polycarbonate is melted and blended with the flame retardant filler to prepare the flame retardant and fireproof plastic.

[0014] The modified filler is prepared by ring-opening octamethylcyclotetrasiloxane and tetramethylcyclotetrasiloxane as raw materials, and then polymerizing with 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane to obtain diamine-terminated polysiloxane, reacting the diamine-terminated polysiloxane with terephthalaldehyde so that the amino groups on the diamine-terminated polysiloxane react with the aldehyde groups on the terephthalaldehyde and are coated on the surface of ammonium polyphosphate to obtain pretreated ammonium phosphate, reacting the pretreated ammonium phosphate with DOPO so that the C=N bond on the pretreated ammonium phosphate is grafted with the PH bond on DOPO to obtain modified ammonium polyphosphate, and reacting the modified ammonium polyphosphate with DOPO to obtain modified ammonium polyphosphate. The modified ammonium polyphosphate is reacted with methacryloyloxypropylmethyldichlorosilane so that Si-H on the modified ammonium polyphosphate reacts with the double bond on the methacryloyloxypropylmethyldichlorosilane to obtain functionalized ammonium polyphosphate; 3-aminotriethoxysilane is protected with tert-butyloxycarbonyl chloride to obtain a modified monomer; the modified monomer is hydrolyzed and condensed to form a sodium cyclotetrasiloxane tetrasilanol structure containing a protective group to obtain a modifier; the modifier and the functionalized ammonium polyphosphate are reacted in the presence of triethylamine so that the sodium silanol on the modifier reacts with the chlorine atom site on the functionalized ammonium polyphosphate to obtain a modified filler.

[0015] When the flame retardant and fireproof plastic is burned, the flame retardant filler is heated by the water molecules to evaporate, causing the structure to expand and forming an isolation layer. At the same time, the evaporation of water molecules can take away heat, and the released ammonia can reduce the content of smoke to achieve a flame retardant effect. The generated inorganic acid and phosphate are dehydrated and carbonized, and cooperate with the isolation layer to form a carbon layer with a large interlayer spacing. The organic silicon structure can form Si-C and increase the density of the carbon layer. The internal aluminum ions and magnesium ions can form aluminum oxide and magnesium oxide after high-temperature combustion, thereby increasing the flame retardancy of the carbon layer and improving the flame retardant and fireproof effect of the plastic. DETAILED DESCRIPTION

[0016] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention. Example 1

[0017] A method for preparing a flame retardant and fireproof plastic comprises the following steps: Step A1: Disperse sepiolite in ethanol, stir and add 3-aminopropyltriethoxysilane and deionized water at a speed of 200 r / min and a temperature of 60° C., and react for 2 hours to obtain amination sepiolite; Step A2: uniformly mix the aminated sepiolite, the modified filler and deionized water, perform ultrasound at a frequency of 20 kHz and a temperature of 80° C., add phytic acid, raise the temperature to 90° C., and react for 5 hours to obtain a flame retardant filler; Step A3: Add bisphenol A polycarbonate into an internal mixer, melt it at a speed of 60 r / min and a temperature of 240° C., add flame retardant filler, melt blend for 8 minutes, hot press and cool to obtain flame retardant and fireproof plastic.

[0018] The amount of 3-aminopropyltriethoxysilane used in step A1 is 3% of the mass of sepiolite.

[0019] The usage ratio of the amination sepiolite, modified filler and phytic acid described in step A2 is 3g0:5g:10mL.

[0020] The mass ratio of the bisphenol A polycarbonate and the flame retardant filler in step A3 is 100:10-15, and the model of the bisphenol A polycarbonate is 25037-45-0.

[0021] The modified filler is prepared by the following steps: Step B1: octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, tetramethylammonium hydroxide, 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane and dimethyl sulfoxide are mixed uniformly, nitrogen is introduced for protection, and the mixture is reacted for 3 hours at a speed of 120 r / min and a temperature of 105° C. to obtain diamine-terminated polysiloxane; ammonium polyphosphate, terephthalaldehyde and DMF are mixed uniformly, stirred at a speed of 150 r / min and a temperature of 65° C., and the diamine-terminated polysiloxane is added, and the mixture is reacted for 8 hours to obtain pretreated ammonium polyphosphate; Step B2: DOPO was dissolved in ethanol, nitrogen was introduced for protection, azobisisobutyronitrile and pretreated ammonium polyphosphate were added under stirring at a speed of 120 r / min and a temperature of 65°C, and the mixture was reacted for 20 hours to obtain modified ammonium polyphosphate, and the modified ammonium polyphosphate, methacryloyloxypropylmethyldichlorosilane, chloroplatinic acid and DMF were uniformly mixed, nitrogen was introduced for protection, and the mixture was reacted for 4 hours at a speed of 60 r / min and a temperature of 75°C to obtain functionalized ammonium polyphosphate; Step B3: 3-aminopropyltriethoxysilane, tert-butyloxycarbonyl chloride and DMF were mixed evenly, and triethylamine was added under the conditions of a rotation speed of 120 r / min and a temperature of 30° C., and the mixture was reacted for 4 hours to obtain a modified monomer, and the modified monomer, isopropanol, deionized water and sodium hydroxide were mixed, and the mixture was reacted for 3 hours under the conditions of a rotation speed of 60 r / min and a temperature of 85° C., and then the mixture was cooled to 20° C. and reacted for 14 hours to obtain a modifier; Step B4: Evenly mix the modifier, triethylamine and tetrahydrofuran, introduce nitrogen protection, stir and add functionalized ammonium polyphosphate at a speed of 120 r / min and a temperature of 0°C, react for 3 hours, heat to 20°C, react for 20 hours to obtain a precursor, disperse the precursor in tetrahydrofuran, stir and add zinc bromide at a speed of 120 r / min and a temperature of 10°C, stir for 3 hours to obtain a modified filler.

[0022] The molar ratio of octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, tetramethylammonium hydroxide and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane described in step B1 is 1.4:1:3:2, and the molar ratio of ammonium polyphosphate, terephthalaldehyde and diamine-terminated polysiloxane is 4 g:5 mmol:5 mmol.

[0023] The molar ratio of the C=N bond on the pretreated ammonium polyphosphate described in step B2 to DOPO is 1:1, the amount of azobisisobutyronitrile is 1‰ of the mass of DOPO, the molar ratio of the Si-H bond on the modified ammonium polyphosphate to methacryloxypropylmethyldichlorosilane is 1:1, and the amount of chloroplatinic acid is 1‰ of the mass of methacryloxypropylmethyldichlorosilane.

[0024] The molar ratio of 3-aminopropyltriethoxysilane, tert-butyloxycarbonyl chloride and triethylamine in step B3 is 1:1:1, and the amount ratio of modified monomer, isopropanol, deionized water and sodium hydroxide is 120mmol:120mL:3mL:80mmol.

[0025] The amount ratio of the modifier, triethylamine, tetrahydrofuran and functionalized ammonium polyphosphate described in step B4 is 8g:5mL:30mL:3g, and the amount ratio of the precursor, tetrahydrofuran and zinc bromide is 3g:20mL:1g. Example 2

[0026] A method for preparing a flame retardant and fireproof plastic comprises the following steps: Step A1: Disperse sepiolite in ethanol, stir and add 3-aminopropyltriethoxysilane and deionized water at a speed of 200 r / min and a temperature of 65° C., and react for 2.5 hours to obtain amination sepiolite; Step A2: the aminated sepiolite, the modified filler and the deionized water are uniformly mixed, ultrasonicated at a frequency of 25 kHz and a temperature of 85° C., phytic acid is added, the temperature is raised to 90° C., and the reaction is carried out for 6 hours to obtain a flame retardant filler; Step A3: Add bisphenol A polycarbonate into an internal mixer, melt it at a speed of 60 r / min and a temperature of 245° C., add a flame retardant filler, melt blend for 9 minutes, hot press and cool to obtain a flame retardant and fireproof plastic.

[0027] The amount of 3-aminopropyltriethoxysilane used in step A1 is 3% of the mass of sepiolite.

[0028] The usage ratio of the amination sepiolite, modified filler and phytic acid described in step A2 is 3g0:5g:10mL.

[0029] The mass ratio of the bisphenol A polycarbonate and the flame retardant filler in step A3 is 100:13, and the model of the bisphenol A polycarbonate is 25037-45-0.

[0030] The modified filler is prepared by the following steps: Step B1: octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, tetramethylammonium hydroxide, 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane and dimethyl sulfoxide are mixed uniformly, nitrogen is introduced for protection, and the mixture is reacted for 4 hours at a speed of 120 r / min and a temperature of 110° C. to obtain diamine-terminated polysiloxane; ammonium polyphosphate, terephthalaldehyde and DMF are mixed uniformly, stirred at a speed of 200 r / min and a temperature of 65° C., and the diamine-terminated polysiloxane is added, and the mixture is reacted for 9 hours to obtain pretreated ammonium polyphosphate; Step B2: DOPO was dissolved in ethanol, nitrogen was introduced for protection, azobisisobutyronitrile and pretreated ammonium polyphosphate were added under stirring at a speed of 150 r / min and a temperature of 65°C, and the mixture was reacted for 25 hours to obtain modified ammonium polyphosphate, and the modified ammonium polyphosphate, methacryloyloxypropylmethyldichlorosilane, chloroplatinic acid and DMF were mixed evenly, nitrogen was introduced for protection, and the mixture was reacted for 5 hours at a speed of 60 r / min and a temperature of 80°C to obtain functionalized ammonium polyphosphate; Step B3: 3-aminopropyltriethoxysilane, tert-butyloxycarbonyl chloride and DMF were mixed evenly, and triethylamine was added under the conditions of a rotation speed of 150 r / min and a temperature of 35° C., and the mixture was reacted for 5 h to obtain a modified monomer; the modified monomer, isopropanol, deionized water and sodium hydroxide were mixed, and the mixture was reacted for 4 h under the conditions of a rotation speed of 60 r / min and a temperature of 90° C., and then the mixture was cooled to 20° C. and reacted for 15 h to obtain a modifier; Step B4: Evenly mix the modifier, triethylamine and tetrahydrofuran, introduce nitrogen protection, stir and add functionalized ammonium polyphosphate at a speed of 150 r / min and a temperature of 0°C, react for 4 hours, then heat to 20°C and react for 25 hours to obtain a precursor, disperse the precursor in tetrahydrofuran, stir and add zinc bromide at a speed of 120 r / min and a temperature of 15°C, and stir for 4 hours to obtain a modified filler.

[0031] The molar ratio of octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, tetramethylammonium hydroxide and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane described in step B1 is 1.4:1:3:2, and the molar ratio of ammonium polyphosphate, terephthalaldehyde and diamine-terminated polysiloxane is 4 g:5 mmol:5 mmol.

[0032] The molar ratio of the C=N bond on the pretreated ammonium polyphosphate described in step B2 to DOPO is 1:1, the amount of azobisisobutyronitrile is 1‰ of the mass of DOPO, the molar ratio of the Si-H bond on the modified ammonium polyphosphate to methacryloxypropylmethyldichlorosilane is 1:1, and the amount of chloroplatinic acid is 1‰ of the mass of methacryloxypropylmethyldichlorosilane.

[0033] The molar ratio of 3-aminopropyltriethoxysilane, tert-butyloxycarbonyl chloride and triethylamine in step B3 is 1:1:1, and the amount ratio of modified monomer, isopropanol, deionized water and sodium hydroxide is 120mmol:120mL:3mL:80mmol.

[0034] The amount ratio of the modifier, triethylamine, tetrahydrofuran and functionalized ammonium polyphosphate described in step B4 is 8g:5mL:30mL:3g, and the amount ratio of the precursor, tetrahydrofuran and zinc bromide is 3g:20mL:1g. Example 3

[0035] A method for preparing a flame retardant and fireproof plastic comprises the following steps: Step A1: Disperse sepiolite in ethanol, stir and add 3-aminopropyltriethoxysilane and deionized water at a speed of 300 r / min and a temperature of 70° C., and react for 3 hours to obtain amination sepiolite; Step A2: uniformly mix the aminated sepiolite, the modified filler and deionized water, perform ultrasound at a frequency of 30 kHz and a temperature of 85° C., add phytic acid, raise the temperature to 95° C., and react for 7 hours to obtain a flame retardant filler; Step A3: Add bisphenol A polycarbonate into an internal mixer, melt it at a speed of 80 r / min and a temperature of 250° C., add flame retardant filler, melt blend for 10 minutes, hot press and cool to obtain flame retardant and fireproof plastic.

[0036] The amount of 3-aminopropyltriethoxysilane used in step A1 is 3% of the mass of sepiolite.

[0037] The usage ratio of the amination sepiolite, modified filler and phytic acid described in step A2 is 3g0:5g:10mL.

[0038] The mass ratio of the bisphenol A polycarbonate and the flame retardant filler in step A3 is 100:15, and the model of the bisphenol A polycarbonate is 25037-45-0.

[0039] The modified filler is prepared by the following steps: Step B1: octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, tetramethylammonium hydroxide, 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane and dimethyl sulfoxide are mixed uniformly, nitrogen is introduced for protection, and the mixture is reacted for 5 hours at a speed of 150 r / min and a temperature of 110° C. to obtain diamine-terminated polysiloxane; ammonium polyphosphate, terephthalaldehyde and DMF are mixed uniformly, stirred at a speed of 200 r / min and a temperature of 70° C., and the diamine-terminated polysiloxane is added, and the mixture is reacted for 10 hours to obtain pretreated ammonium polyphosphate; Step B2: DOPO was dissolved in ethanol, nitrogen was introduced for protection, azobisisobutyronitrile and pretreated ammonium polyphosphate were added under stirring at a speed of 150 r / min and a temperature of 70°C, and the mixture was reacted for 25 hours to obtain modified ammonium polyphosphate, and the modified ammonium polyphosphate, methacryloyloxypropylmethyldichlorosilane, chloroplatinic acid and DMF were uniformly mixed, nitrogen was introduced for protection, and the mixture was reacted for 6 hours at a speed of 80 r / min and a temperature of 80°C to obtain functionalized ammonium polyphosphate; Step B3: 3-aminopropyltriethoxysilane, tert-butyloxycarbonyl chloride and DMF were mixed evenly, and triethylamine was added under the conditions of a rotation speed of 150 r / min and a temperature of 40° C., and the mixture was reacted for 6 hours to obtain a modified monomer, and the modified monomer, isopropanol, deionized water and sodium hydroxide were mixed, and the mixture was reacted for 5 hours under the conditions of a rotation speed of 80 r / min and a temperature of 90° C., and then the mixture was cooled to 25° C. and reacted for 16 hours to obtain a modifier; Step B4: Evenly mix the modifier, triethylamine and tetrahydrofuran, introduce nitrogen protection, stir and add functionalized ammonium polyphosphate at a speed of 150 r / min and a temperature of 0°C, react for 5 hours, heat to 25°C, react for 25 hours to obtain a precursor, disperse the precursor in tetrahydrofuran, stir and add zinc bromide at a speed of 150 r / min and a temperature of 15°C, stir for 5 hours to obtain a modified filler.

[0040] The molar ratio of octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, tetramethylammonium hydroxide and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane described in step B1 is 1.4:1:3:2, and the molar ratio of ammonium polyphosphate, terephthalaldehyde and diamine-terminated polysiloxane is 4 g:5 mmol:5 mmol.

[0041] The molar ratio of the C=N bond on the pretreated ammonium polyphosphate described in step B2 to DOPO is 1:1, the amount of azobisisobutyronitrile is 1‰ of the mass of DOPO, the molar ratio of the Si-H bond on the modified ammonium polyphosphate to methacryloxypropylmethyldichlorosilane is 1:1, and the amount of chloroplatinic acid is 1‰ of the mass of methacryloxypropylmethyldichlorosilane.

[0042] The molar ratio of 3-aminopropyltriethoxysilane, tert-butyloxycarbonyl chloride and triethylamine in step B3 is 1:1:1, and the amount ratio of modified monomer, isopropanol, deionized water and sodium hydroxide is 120mmol:120mL:3mL:80mmol.

[0043] The amount ratio of the modifier, triethylamine, tetrahydrofuran and functionalized ammonium polyphosphate described in step B4 is 8g:5mL:30mL:3g, and the amount ratio of the precursor, tetrahydrofuran and zinc bromide is 3g:20mL:1g.

[0044] Comparative Example 1 Compared with Example 1, no modified filler was added in this comparative example, and the remaining steps were the same.

[0045] Comparative Example 2 Compared with Example 1, this comparative example did not add amination sepiolite, and the remaining steps were the same.

[0046] Comparative Example 3 Compared with Example 1, this comparative example uses dimethyldichlorosilane to replace the functionalized ammonium polyphosphate, and the remaining steps are the same.

[0047] Comparative Example 4 Compared with Example 1, this comparative example uses modified ammonium polyphosphate to replace the flame retardant filler, and the other steps are the same.

[0048] The plastics obtained in Examples 1-3 and Comparative Examples 1-4 were used to prepare 80 mm × 10 mm × 4 mm samples according to the standard of GB / T2406.2-2009 to detect the limiting oxygen index. 130 mm × 13 mm × 4 mm samples were used to test the vertical burning grade according to the standard of GB / T2408-2021. 100 mm × 100 mm × 4 mm samples were used to calculate the fire performance index in units of 10 -2 s / (kW / m 2 ), the test results are shown in the following table.

[0049] Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Limiting oxygen index% 36.7 36.9 37.2 33.1 35.2 30.1 29.6 Vertical burning level V0 V0 V0 V1 V1 V1 V1 Fire Performance Index 15.17 15.24 15.31 12.73 13.35 10.96 10.88

[0050] It can be seen from the above table that this application has a very good flame retardant and fireproof effect.

[0051] The above contents are merely examples and explanations of the concept of the present invention. The technicians in this technical field may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the concept of the invention or exceed the scope defined by the claims, they should all fall within the protection scope of the present invention.

Claims

1. A method for preparing a flame retardant and fireproof plastic, characterized in that: The specific steps include: Step A1: dispersing sepiolite in ethanol, stirring and adding 3-aminopropyltriethoxysilane and deionized water to react to obtain amination sepiolite; Step A2: mixing the aminated sepiolite, the modified filler and deionized water by ultrasonication, adding phytic acid, and heating to react to obtain a flame retardant filler; Step A3: Add bisphenol A type polycarbonate into an internal mixer, melt it, add flame retardant filler, melt blend, hot press and cool it to obtain flame retardant and fireproof plastic.

2. The method for preparing a flame retardant and fireproof plastic according to claim 1, characterized in that: The amount of 3-aminopropyltriethoxysilane used in step A1 is 3% of the mass of sepiolite.

3. The method for preparing a flame retardant and fireproof plastic according to claim 1, characterized in that: The usage ratio of the amination sepiolite, modified filler and phytic acid described in step A2 is 3g0:5g:10mL.

4. The method for preparing a flame retardant and fireproof plastic according to claim 1, characterized in that: The mass ratio of the bisphenol A polycarbonate to the flame retardant filler in step A3 is 100:10-15.

5. The method for preparing a flame retardant and fireproof plastic according to claim 1, characterized in that: The modified filler is prepared by the following steps: Step B1: octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, tetramethylammonium hydroxide, 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane and dimethyl sulfoxide are uniformly mixed, nitrogen is introduced for protection, and a reaction is carried out to obtain a diamine-terminated polysiloxane; ammonium polyphosphate, terephthalaldehyde and DMF are mixed and stirred, and the diamine-terminated polysiloxane is added to react to obtain a pretreated ammonium polyphosphate; Step B2: dissolving DOPO in ethanol, introducing nitrogen for protection, stirring and adding azobisisobutyronitrile and pretreated ammonium polyphosphate to react to obtain modified ammonium polyphosphate, and uniformly mixing the modified ammonium polyphosphate, methacryloyloxypropylmethyldichlorosilane, chloroplatinic acid and DMF, introducing nitrogen for protection, and reacting to obtain functionalized ammonium polyphosphate; Step B3: 3-aminopropyltriethoxysilane, tert-butyloxycarbonyl chloride and DMF are mixed and stirred, and triethylamine is added to react to obtain a modified monomer, and the modified monomer, isopropanol, deionized water and sodium hydroxide are mixed and reacted, and the temperature is lowered to continue the reaction to obtain a modifier; Step B4: uniformly mix the modifier, triethylamine and tetrahydrofuran, introduce nitrogen protection, stir and add functionalized ammonium polyphosphate, react, increase the temperature and continue the reaction to obtain a precursor, disperse the precursor in tetrahydrofuran, stir and add zinc bromide, stir and treat to obtain a modified filler.

6. The method for preparing a flame retardant and fireproof plastic according to claim 5, characterized in that: The molar ratio of octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, tetramethylammonium hydroxide and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane described in step B1 is 1.4:1:3:2, and the molar ratio of ammonium polyphosphate, terephthalaldehyde and diamine-terminated polysiloxane is 4 g:5 mmol:5 mmol.

7. The method for preparing a flame retardant and fireproof plastic according to claim 5, characterized in that: The molar ratio of the C=N bond on the pretreated ammonium polyphosphate described in step B2 to DOPO is 1:1, and the molar ratio of the Si-H bond on the modified ammonium polyphosphate to methacryloxypropylmethyldichlorosilane is 1:

1.

8. The method for preparing a flame retardant and fireproof plastic according to claim 5, characterized in that: The molar ratio of 3-aminopropyltriethoxysilane, tert-butyloxycarbonyl chloride and triethylamine in step B3 is 1:1:1, and the amount ratio of modified monomer, isopropanol, deionized water and sodium hydroxide is 120mmol:120mL:3mL:80mmol.

9. The method for preparing a flame retardant and fireproof plastic according to claim 5, characterized in that: The amount ratio of the modifier, triethylamine, tetrahydrofuran and functionalized ammonium polyphosphate described in step B4 is 8g:5mL:30mL:3g, and the amount ratio of the precursor, tetrahydrofuran and zinc bromide is 3g:20mL:1g.

10. A flame retardant and fireproof plastic, characterized in that: Prepared according to any one of claims 1 to 9.

Citation Information

Patent Citations

  • Fireproof flame-retardant cable

    CN117603518A

  • Fireproof artificial composite board and preparation method thereof

    CN117801497A

  • Flame-retardant antistatic fiber fabric and preparation method thereof

    CN118241487A

  • Polystyrene composite material and preparation method thereof

    CN118359774A

  • Flame-retardant cable

    CN118374095A

Cited By

  • Flame-retardant regenerated PET composite material and preparation method thereof

    CN120025672A

  • High-temperature-resistant PE electric power pipe and preparation method thereof

    CN120173321A

  • Fire-resistant inorganic fiber cotton board and preparation method thereof

    CN120664852A

  • A fire-resistant inorganic fiber wool board and a method for manufacturing the same

    CN120664852B

  • High-flame-retardant tpe material and preparation method thereof

    CN121226670A