A masterbatch with flame retardant function and preparation method thereof

Abstract

The invention discloses a masterbatch with flame retardant function and a preparation method thereof, belonging to the field of polymer materials. The masterbatch comprises the following raw materials in parts by weight: 100-150 parts of linear low-density polyethylene, 15-25 parts of modified fillers, 2-5 parts of dicumyl peroxide and 10-20 parts of toner. When the masterbatch is burned, the organic silicon structure on the surface of the modified filler can form a silicon-carbon layer containing titanium dioxide. Meanwhile, the modifier contains S, P, B and N elements, which can improve the compactness of the carbon layer. The masterbatch contains an aluminum phosphate structure inside, which absorbs heat during high-temperature decomposition to delay combustion and generate polyphosphates. The polyphosphates can inhibit the generation of smoke and toxic gases. The modified filler has a zinc organic framework inside, which releases carbon dioxide and water vapor under high temperature conditions to reduce oxygen concentration, and forms a porous carbon layer containing zinc oxide inside, which can capture smoke and toxic gases.

Description

Technical Field

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

[0002] In recent years, as people's requirements for environmental protection and safety performance continue to increase, polyethylene (PE) materials are increasingly used in the fields of construction, electronics, wires and cables, etc. However, PE materials themselves are highly flammable and will produce a large amount of harmful gases when burned. Therefore, flame retardancy and smoke suppression performance have become the focus of people's attention. At present, some polyethylene flame retardants on the market are mainly doped by adding flame retardants such as halogens, phosphorus, and oxidized metals. Although these flame retardants can effectively inhibit the combustion of PE materials, there are problems such as environmental pollution, carcinogenicity risks, and peeling. Therefore, it is urgent to develop a new polyethylene flame retardant and smoke suppression masterbatch with excellent performance, environmental protection, and safety. Summary of the invention

[0003] The purpose of the present invention is to provide a masterbatch with flame retardant function and a preparation method thereof, which solves the problem that the current polyethylene masterbatch has poor flame retardant effect and is prone to dripping.

[0004] The purpose of the present invention can be achieved through the following technical solutions:

[0005] A method for preparing a masterbatch with flame retardant function comprises the following steps:

[0006] Weigh the following raw materials in parts by weight: 100-150 parts of linear low-density polyethylene, 15-25 parts of modified filler, 2-5 parts of dicumyl peroxide and 10-20 parts of toner;

[0007] The raw materials are added into a twin-screw extruder, and extruded, cooled and granulated under the conditions of 80°C in the first zone, 130°C in the second zone, 180°C in the third zone, 230°C in the fourth zone, 230°C in the fifth zone and 230°C in the die head to obtain a masterbatch with flame retardant function.

[0008] Further, the modified filler is prepared by the following steps:

[0009] Step A1: zinc nitrate hexahydrate, 2-aminoterephthalic acid and DMF are mixed evenly, triethylamine is added, and the mixture is reacted for 20-25 hours at a speed of 200-300 r / min and a temperature of 100° C. to obtain a zinc organic framework; zinc organic framework, KH560 and toluene are mixed evenly, nitrogen is introduced to replace air, and triethylamine is added to the mixture at a speed of 120-150 r / min and a temperature of 10-15° C. to obtain a pretreated organic framework;

[0010] Step A2: The pretreated organic framework, acrylic acid, p-toluenesulfonic acid and toluene are mixed evenly, nitrogen is introduced to replace the air, and the reaction is carried out for 6-8 hours at a speed of 60-80 r / min and a temperature of 110-120° C. to obtain a modified organic framework; sodium hypophosphite and acetic acid are mixed evenly, nitrogen is introduced to replace the air, and tert-butyl peroxide and concentrated sulfuric acid are added under stirring at a speed of 120-150 r / min and a temperature of 70-80° C., the temperature is raised to 110-115° C., the modified organic framework is added, and the reaction is carried out for 40-45 hours to obtain a precursor;

[0011] Step A3: Disperse the precursor in ethanol, introduce nitrogen to remove air, adjust the pH value to 4-5, add aluminum sulfate at a speed of 200-300r / min and a temperature of 70-75°C, and react for 1-1.5h to obtain a modified precursor; disperse the modified precursor in ethanol, add methyltrimethoxysilane, modifier, KH570 and tetrabutyl titanate, stir and add hydrochloric acid solution and deionized water at a speed of 150-200r / min and a temperature of 50-60°C, react for 3-5h, heat to 110-120°C, and keep warm for 6-8h to obtain a modified filler.

[0012] Furthermore, the amount ratio of zinc nitrate hexahydrate, 2-aminoterephthalic acid, DMF and triethylamine described in step A1 is 16mmol:8mmol:10mL:1mL, the molar ratio of amino groups on the zinc organic framework and KH560 is 1:2, and the volume ratio of KH560 and toluene is 1:5.

[0013] Furthermore, the molar ratio of hydroxyl groups and acrylic acid on the pretreated organic framework in step A2 is 1:1, the amount of p-toluenesulfonic acid is 1% of the mass of acrylic acid, the amount ratio of acrylic acid to toluene is 1g:8mL, the amount ratio of sodium hypophosphite, acetic acid, tert-butyl peroxide, concentrated sulfuric acid and modified organic framework is 15g:25mL:1g:2g:20g, and the mass fraction of concentrated sulfuric acid is 70%.

[0014] Furthermore, the amount ratio of the precursor, ethanol and aluminum sulfate described in step A3 is 3g:10mL:1g, the amount ratio of the modified precursor, ethanol, methyltrimethoxysilane, modifier, KH570, tetrabutyl titanate, hydrochloric acid solution and deionized water is 2g:20mL:4mL:0.5g:2mL:1mL:3mL:5mL, and the mass fraction of the hydrochloric acid solution is 10%.

[0015] Further, the modifier is prepared by the following steps:

[0016] Step B1: Mix cyanuric chloride, 2,6,7-trioxa-1-phosphabicyclo (2.2.2) octane-4-methanol-1-oxide, triethylamine and tetrahydrofuran, react for 3-5 hours at a speed of 120-150 r / min and a temperature of 40-50° C., add diethanolamine, raise the temperature to 80-90° C., and reflux for 2-3 hours to obtain intermediate 1;

[0017] Step B2: Intermediate 1, 4-formylphenylboric acid, tributyl metaphosphate and toluene are mixed, and refluxed for reaction for 4-6 hours at a speed of 120-150 r / min and a temperature of 110-120° C. to obtain intermediate 2; intermediate 2, KH550 and ethanol are mixed evenly, nitrogen is introduced for protection, and refluxed for reaction for 5-7 hours at a speed of 60-80 r / min and a temperature of 80-85° C., DOPO is added, and the reaction is continued for 10-15 hours to obtain a modifier.

[0018] Furthermore, the amount ratio of cyanuric chloride, 2,6,7-trioxa-1-phosphabicyclo (2.2.2) octane-4-methanol-1-oxide, triethylamine, tetrahydrofuran and diethanolamine in step B1 is 1 mmol:2 mmol:3.1 mmol:20 mL:1.2 mmol.

[0019] Furthermore, the amount ratio of the intermediate 1, 4-formylphenylboric acid and toluene in step B2 is 1mmol:1mmol:5mL, the amount of tributyl metaphosphate is 1.5% by mass of 4-formylphenylboronic acid, and the amount ratio of the intermediate 2, KH550, ethanol and DOPO is 1mmol:1mmol:15mL:1.2mmol.

[0020] The invention has the beneficial effects as follows: a color masterbatch with flame retardant function prepared by the invention comprises the following raw materials: linear low-density polyethylene, modified filler, diisopropylbenzene peroxide and color powder; the modified filler is reacted with zinc nitrate hexahydrate and 2-aminoterephthalic acid as raw materials to obtain a zinc organic framework; the zinc organic framework is treated with KH560 so that the amino groups on the zinc organic framework react with the epoxy groups on the KH560 to obtain a pretreated organic framework; the pretreated organic framework is reacted with acrylic acid so that the hydroxyl groups on the pretreated organic framework are esterified with acrylic acid to obtain a modified organic framework; sodium hypophosphite is reacted with the modified organic framework so that the PH bond on the sodium hypophosphite is grafted with the double bond on the modified organic framework, and under the action of concentrated sulfuric acid, the sodium phosphate is converted into phosphoric acid to obtain a precursor; the precursor is reacted with aluminum sulfate so that the phosphoric acid on the precursor reacts with the aluminum ion in the aluminum sulfate to form an aluminum phosphate structure to obtain a modified precursor; the modified precursor, the modifier, KH570 and tetrabutyl titanate are hydrolyzed and condensed to obtain a modified filler.

[0021] The modifier uses cyanuric chloride and 2,6,7-trioxa-1-phosphabicyclo (2.2.2) octane-4-methanol-1-oxide as raw materials. By controlling the temperature, two chlorine atoms on the cyanuric chloride react with hydroxyl groups on 2,6,7-trioxa-1-phosphabicyclo (2.2.2) octane-4-methanol-1-oxide. Then the temperature is raised and diethanolamine is added to react the remaining chlorine atoms with the secondary amine on the diethanolamine to obtain an intermediate 1. The intermediate 1 is reacted with 4-formylphenylboronic acid to react the hydroxyl group on the intermediate 1 with the boronic acid group on the 4-formylphenylboronic acid to obtain an intermediate 2. The intermediate 2 is reacted with KH550 to react the aldehyde group on the intermediate 2 with the amino group on KH550 to form a C=N bond. The C=N bond then reacts with DOPO to obtain the modifier.

[0022] When the masterbatch is burned, the organic silicon structure on the surface of the modified filler can form a silicon-carbon layer containing titanium dioxide. At the same time, the modifier contains S, P, B and N elements. The S element can produce sulfuric acid at high temperature, and then the masterbatch molecular material produces a carbon layer at this time, which cooperates with the P, B and N elements to further improve the density of the carbon layer. The interior contains an aluminum phosphate structure, which absorbs heat during high-temperature decomposition, thereby delaying combustion and producing polyphosphates. Polyphosphates can inhibit the generation of smoke and toxic gases. The interior of the modified filler is a zinc organic framework, which releases carbon dioxide and water vapor under high temperature conditions, thereby reducing the oxygen concentration and forming a porous carbon layer containing zinc oxide inside, which can capture smoke and toxic gases. The various types of multi-layer barrier layers formed by the modified filler can well prevent the spread of flames and avoid dripping. DETAILED DESCRIPTION

[0023] 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.

[0024] Embodiment 1: A method for preparing a masterbatch with flame retardant function, comprising the following steps:

[0025] Weigh the following raw materials in parts by weight: 100 parts of linear low-density polyethylene, 15 parts of modified filler, 2 parts of dicumyl peroxide and 10 parts of toner;

[0026] The raw materials are added into a twin-screw extruder, and extruded, cooled and granulated under the conditions of 80°C in the first zone, 130°C in the second zone, 180°C in the third zone, 230°C in the fourth zone, 230°C in the fifth zone and 230°C in the die head to obtain a masterbatch with flame retardant function.

[0027] The density of the linear low-density polyethylene is 0.939 g·cm -3 , melt index 5.8g·(10min) -1 .

[0028] The modified filler is prepared by the following steps:

[0029] Step A1: zinc nitrate hexahydrate, 2-aminoterephthalic acid and DMF are mixed evenly, triethylamine is added, and the reaction is carried out at a speed of 200 r / min and a temperature of 100° C. for 20 hours to obtain a zinc organic framework; zinc organic framework, KH560 and toluene are mixed evenly, nitrogen is introduced to replace the air, and triethylamine is added to stir at a speed of 120 r / min and a temperature of 10° C. until the pH value is 8, and the reaction is carried out for 3 hours to obtain a pretreated organic framework;

[0030] Step A2: The pretreated organic framework, acrylic acid, p-toluenesulfonic acid and toluene are mixed evenly, nitrogen is introduced to replace the air, and the reaction is carried out for 6 hours at a speed of 60 r / min and a temperature of 110° C. to obtain a modified organic framework; sodium hypophosphite and acetic acid are mixed evenly, nitrogen is introduced to replace the air, and tert-butyl peroxide and concentrated sulfuric acid are added under stirring at a speed of 120 r / min and a temperature of 70° C., the temperature is raised to 110° C., the modified organic framework is added, and the reaction is carried out for 40 hours to obtain a precursor;

[0031] Step A3: Disperse the precursor in ethanol, introduce nitrogen to remove air, adjust the pH value to 4, add aluminum sulfate at a speed of 200 r / min and a temperature of 70°C, and react for 1 hour to obtain a modified precursor; disperse the modified precursor in ethanol, add methyltrimethoxysilane, modifier, KH570 and tetrabutyl titanate, stir and add hydrochloric acid solution and deionized water at a speed of 150 r / min and a temperature of 50°C, react for 3 hours, heat to 110°C, and keep warm for 6 hours to obtain a modified filler.

[0032] The amount ratio of zinc nitrate hexahydrate, 2-aminoterephthalic acid, DMF and triethylamine described in step A1 is 16mmol:8mmol:10mL:1mL, the molar ratio of amino groups on the zinc organic framework and KH560 is 1:2, and the volume ratio of KH560 and toluene is 1:5.

[0033] The molar ratio of hydroxyl groups and acrylic acid on the pretreated organic framework described in step A2 is 1:1, the amount of p-toluenesulfonic acid is 1% of the mass of acrylic acid, the amount ratio of acrylic acid and toluene is 1g:8mL, the amount ratio of sodium hypophosphite, acetic acid, tert-butyl peroxide, concentrated sulfuric acid and modified organic framework is 15g:25mL:1g:2g:20g, and the mass fraction of concentrated sulfuric acid is 70%.

[0034] The amount ratio of the precursor, ethanol and aluminum sulfate described in step A3 is 3g:10mL:1g, the amount ratio of the modified precursor, ethanol, methyltrimethoxysilane, modifier, KH570, tetrabutyl titanate, hydrochloric acid solution and deionized water is 2g:20mL:4mL:0.5g:2mL:1mL:3mL:5mL, and the mass fraction of the hydrochloric acid solution is 10%.

[0035] The modifier is prepared by the following steps:

[0036] Step B1: Mix cyanuric chloride, 2,6,7-trioxa-1-phosphabicyclo (2.2.2) octane-4-methanol-1-oxide, triethylamine and tetrahydrofuran, react for 3 hours at a speed of 120 r / min and a temperature of 40° C., add diethanolamine, raise the temperature to 80° C., and reflux for 2 hours to obtain intermediate 1;

[0037] Step B2: Intermediate 1, 4-formylphenylboric acid, tributyl metaphosphate and toluene are mixed, and refluxed for reaction at a speed of 120 r / min and a temperature of 110° C. for 4 hours to obtain intermediate 2; intermediate 2, KH550 and ethanol are mixed evenly, nitrogen is introduced for protection, and refluxed for reaction at a speed of 60 r / min and a temperature of 80° C. for 5 hours, DOPO is added, and the reaction is continued for 10 hours to obtain a modifier.

[0038] The amount ratio of cyanuric chloride, 2,6,7-trioxa-1-phosphabicyclo (2.2.2) octane-4-methanol-1-oxide, triethylamine, tetrahydrofuran and diethanolamine described in step B1 is 1 mmol:2 mmol:3.1 mmol:20 mL:1.2 mmol.

[0039] The amount ratio of intermediate 1, 4-formylphenylboric acid and toluene in step B2 is 1mmol:1mmol:5mL, the amount of tributyl metaphosphate is 1.5% of the mass of 4-formylphenylboronic acid, and the amount ratio of intermediate 2, KH550, ethanol and DOPO is 1mmol:1mmol:15mL:1.2mmol.

[0040] Embodiment 2: A method for preparing a masterbatch with flame retardant function, comprising the following steps:

[0041] Weigh the following raw materials in parts by weight: 130 parts of linear low-density polyethylene, 20 parts of modified filler, 3.5 parts of dicumyl peroxide and 15 parts of toner;

[0042] The raw materials are added into a twin-screw extruder, and extruded, cooled and granulated under the conditions of 80°C in the first zone, 130°C in the second zone, 180°C in the third zone, 230°C in the fourth zone, 230°C in the fifth zone and 230°C in the die head to obtain a masterbatch with flame retardant function.

[0043] The density of the linear low-density polyethylene is 0.939 g·cm -3 , melt index 5.8g·(10min) -1 .

[0044] The modified filler is prepared by the following steps:

[0045] Step A1: zinc nitrate hexahydrate, 2-aminoterephthalic acid and DMF are mixed evenly, triethylamine is added, and the mixture is reacted for 25 hours at a speed of 200 r / min and a temperature of 100° C. to obtain a zinc organic framework; zinc organic framework, KH560 and toluene are mixed evenly, nitrogen is introduced to replace the air, and triethylamine is added to the mixture at a speed of 120 r / min and a temperature of 15° C. to obtain a pretreated organic framework;

[0046] Step A2: The pretreated organic framework, acrylic acid, p-toluenesulfonic acid and toluene are mixed evenly, nitrogen is introduced to replace the air, and the reaction is carried out for 7 hours at a speed of 80 r / min and a temperature of 115° C. to obtain a modified organic framework; sodium hypophosphite and acetic acid are mixed evenly, nitrogen is introduced to replace the air, and tert-butyl peroxide and concentrated sulfuric acid are added under stirring at a speed of 120 r / min and a temperature of 75° C., the temperature is raised to 115° C., the modified organic framework is added, and the reaction is carried out for 40 hours to obtain a precursor;

[0047] Step A3: Disperse the precursor in ethanol, introduce nitrogen to remove air, adjust the pH value to 5, add aluminum sulfate at a speed of 200 r / min and a temperature of 75°C, and react for 1 hour to obtain a modified precursor; disperse the modified precursor in ethanol, add methyltrimethoxysilane, modifier, KH570 and tetrabutyl titanate, stir and add hydrochloric acid solution and deionized water at a speed of 200 r / min and a temperature of 55°C, react for 4 hours, heat to 115°C, and keep warm for 7 hours to obtain a modified filler.

[0048] The amount ratio of zinc nitrate hexahydrate, 2-aminoterephthalic acid, DMF and triethylamine described in step A1 is 16mmol:8mmol:10mL:1mL, the molar ratio of amino groups on the zinc organic framework and KH560 is 1:2, and the volume ratio of KH560 and toluene is 1:5.

[0049] The molar ratio of hydroxyl groups and acrylic acid on the pretreated organic framework described in step A2 is 1:1, the amount of p-toluenesulfonic acid is 1% of the mass of acrylic acid, the amount ratio of acrylic acid and toluene is 1g:8mL, the amount ratio of sodium hypophosphite, acetic acid, tert-butyl peroxide, concentrated sulfuric acid and modified organic framework is 15g:25mL:1g:2g:20g, and the mass fraction of concentrated sulfuric acid is 70%.

[0050] The amount ratio of the precursor, ethanol and aluminum sulfate described in step A3 is 3g:10mL:1g, the amount ratio of the modified precursor, ethanol, methyltrimethoxysilane, modifier, KH570, tetrabutyl titanate, hydrochloric acid solution and deionized water is 2g:20mL:4mL:0.5g:2mL:1mL:3mL:5mL, and the mass fraction of the hydrochloric acid solution is 10%.

[0051] The modifier is prepared by the following steps:

[0052] Step B1: Cyanuric chloride, 2,6,7-trioxa-1-phosphabicyclo (2.2.2) octane-4-methanol-1-oxide, triethylamine and tetrahydrofuran are mixed, and the mixture is reacted at a speed of 150 r / min and a temperature of 45° C. for 4 h, and diethanolamine is added, the temperature is raised to 85° C., and the mixture is refluxed for 3 h to obtain intermediate 1;

[0053] Step B2: Intermediate 1, 4-formylphenylboric acid, tributyl metaphosphate and toluene are mixed, and refluxed for reaction at a speed of 150 r / min and a temperature of 115° C. for 4-6 hours to obtain intermediate 2; intermediate 2, KH550 and ethanol are mixed evenly, nitrogen is introduced for protection, and refluxed for reaction at a speed of 60-80 r / min and a temperature of 80-85° C. for 5-7 hours, DOPO is added, and the reaction is continued for 10-15 hours to obtain a modifier.

[0054] The amount ratio of cyanuric chloride, 2,6,7-trioxa-1-phosphabicyclo (2.2.2) octane-4-methanol-1-oxide, triethylamine, tetrahydrofuran and diethanolamine described in step B1 is 1 mmol:2 mmol:3.1 mmol:20 mL:1.2 mmol.

[0055] The amount ratio of intermediate 1, 4-formylphenylboric acid and toluene in step B2 is 1mmol:1mmol:5mL, the amount of tributyl metaphosphate is 1.5% of the mass of 4-formylphenylboronic acid, and the amount ratio of intermediate 2, KH550, ethanol and DOPO is 1mmol:1mmol:15mL:1.2mmol.

[0056] Embodiment 3: A method for preparing a masterbatch with flame retardant function, comprising the following steps:

[0057] Weigh the following raw materials in parts by weight: 150 parts of linear low-density polyethylene, 25 parts of modified filler, 5 parts of dicumyl peroxide and 20 parts of toner;

[0058] The raw materials are added into a twin-screw extruder, and extruded, cooled and granulated under the conditions of 80°C in the first zone, 130°C in the second zone, 180°C in the third zone, 230°C in the fourth zone, 230°C in the fifth zone and 230°C in the die head to obtain a masterbatch with flame retardant function.

[0059] The density of the linear low-density polyethylene is 0.939 g·cm -3 , melt index 5.8g·(10min) -1 .

[0060] The modified filler is prepared by the following steps:

[0061] Step A1: zinc nitrate hexahydrate, 2-aminoterephthalic acid and DMF are mixed evenly, triethylamine is added, and the mixture is reacted for 25 hours at a speed of 300 r / min and a temperature of 100° C. to obtain a zinc organic framework; zinc organic framework, KH560 and toluene are mixed evenly, nitrogen is introduced to replace the air, and triethylamine is added to the mixture at a speed of 150 r / min and a temperature of 15° C. to obtain a pretreated organic framework;

[0062] Step A2: The pretreated organic framework, acrylic acid, p-toluenesulfonic acid and toluene are mixed evenly, nitrogen is introduced to replace the air, and the reaction is carried out for 8 hours at a speed of 80 r / min and a temperature of 120° C. to obtain a modified organic framework; sodium hypophosphite and acetic acid are mixed evenly, nitrogen is introduced to replace the air, and tert-butyl peroxide and concentrated sulfuric acid are added under stirring at a speed of 150 r / min and a temperature of 80° C., the temperature is raised to 115° C., the modified organic framework is added, and the reaction is carried out for 45 hours to obtain a precursor;

[0063] Step A3: Disperse the precursor in ethanol, introduce nitrogen to remove air, adjust the pH value to 5, add aluminum sulfate at a speed of 300 r / min and a temperature of 75°C, and react for 1.5 hours to obtain a modified precursor; disperse the modified precursor in ethanol, add methyltrimethoxysilane, modifier, KH570 and tetrabutyl titanate, stir and add hydrochloric acid solution and deionized water at a speed of 200 r / min and a temperature of 60°C, react for 5 hours, heat to 120°C, and keep warm for 8 hours to obtain a modified filler.

[0064] The amount ratio of zinc nitrate hexahydrate, 2-aminoterephthalic acid, DMF and triethylamine described in step A1 is 16mmol:8mmol:10mL:1mL, the molar ratio of amino groups on the zinc organic framework and KH560 is 1:2, and the volume ratio of KH560 and toluene is 1:5.

[0065] The molar ratio of hydroxyl groups and acrylic acid on the pretreated organic framework described in step A2 is 1:1, the amount of p-toluenesulfonic acid is 1% of the mass of acrylic acid, the amount ratio of acrylic acid and toluene is 1g:8mL, the amount ratio of sodium hypophosphite, acetic acid, tert-butyl peroxide, concentrated sulfuric acid and modified organic framework is 15g:25mL:1g:2g:20g, and the mass fraction of concentrated sulfuric acid is 70%.

[0066] The amount ratio of the precursor, ethanol and aluminum sulfate described in step A3 is 3g:10mL:1g, the amount ratio of the modified precursor, ethanol, methyltrimethoxysilane, modifier, KH570, tetrabutyl titanate, hydrochloric acid solution and deionized water is 2g:20mL:4mL:0.5g:2mL:1mL:3mL:5mL, and the mass fraction of the hydrochloric acid solution is 10%.

[0067] The modifier is prepared by the following steps:

[0068] Step B1: Cyanuric chloride, 2,6,7-trioxa-1-phosphabicyclo (2.2.2) octane-4-methanol-1-oxide, triethylamine and tetrahydrofuran are mixed, and the mixture is reacted at a speed of 150 r / min and a temperature of 50° C. for 5 h, and diethanolamine is added, the temperature is raised to 90° C., and the mixture is refluxed for 3 h to obtain intermediate 1;

[0069] Step B2: Intermediate 1, 4-formylphenylboric acid, tributyl metaphosphate and toluene are mixed, and refluxed for 6 hours at a speed of 150 r / min and a temperature of 120° C. to obtain intermediate 2; intermediate 2, KH550 and ethanol are mixed evenly, nitrogen is introduced for protection, and refluxed for 7 hours at a speed of 80 r / min and a temperature of 85° C., DOPO is added, and the reaction is continued for 15 hours to obtain a modifier.

[0070] The amount ratio of cyanuric chloride, 2,6,7-trioxa-1-phosphabicyclo (2.2.2) octane-4-methanol-1-oxide, triethylamine, tetrahydrofuran and diethanolamine described in step B1 is 1 mmol:2 mmol:3.1 mmol:20 mL:1.2 mmol.

[0071] The amount ratio of intermediate 1, 4-formylphenylboric acid and toluene in step B2 is 1mmol:1mmol:5mL, the amount of tributyl metaphosphate is 1.5% of the mass of 4-formylphenylboronic acid, and the amount ratio of intermediate 2, KH550, ethanol and DOPO is 1mmol:1mmol:15mL:1.2mmol.

[0072] Comparative Example 1:

[0073] Compared with Example 1, no modifier was added in this comparative example, and the remaining steps were the same.

[0074] Comparative Example 2:

[0075] Compared with Example 1, in this comparative example, cyanuric chloride, 2,6,7-trioxa-1-phosphabicyclo (2.2.2) octane-4-methanol-1-oxide, triethylamine and tetrahydrofuran were mixed, and the reaction was carried out for 3 hours at a speed of 120 r / min and a temperature of 40°C. KH550 was added, the temperature was raised to 80°C, and the reaction was refluxed for 2 hours. The obtained product replaced the modifier, and the remaining steps were the same.

[0076] Comparative Example 3:

[0077] Compared with Example 1, this comparative example uses a pretreated organic framework instead of a modified precursor, and the remaining steps are the same.

[0078] The masterbatches prepared in Examples 1-3 and Comparative Examples 1-3 were tested for combustion grade according to the standard of GB / T2048-2021, with a sample size of 125 mm × 13 mm × 3 mm. The limit oxygen index was tested according to the standard of GB / T2406.2-2009, with a sample size of 150 mm × 10 mm × 4 mm. The smoke density was tested according to the standard of GB / T8323.2-2008, with a square sample size of 75 mm and a thickness of 25 mm. The test results are shown in Table 1.

[0079] Table 1 Test results of masterbatches obtained from Examples 1-3 and Comparative Examples 1-3:

[0080] It can be seen from the above table that the present invention has a very good flame retardant and smoke suppression effect.

[0081] 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 masterbatch with flame retardant function, characterized in that: The specific steps include: Weigh the following raw materials in parts by weight: 100-150 parts of linear low-density polyethylene, 15-25 parts of modified filler, 2-5 parts of dicumyl peroxide and 10-20 parts of toner; The raw materials are added into a twin-screw extruder, and the temperature of the first zone is 80°C, the temperature of the second zone is 130°C, the temperature of the third zone is 180°C, the temperature of the fourth zone is 230°C, the temperature of the fifth zone is 230°C, and the temperature of the die head is 230°C. The raw materials are extruded, cooled, and granulated to obtain a masterbatch with a flame retardant function. The modified filler is prepared by the following steps: Step A1: zinc nitrate hexahydrate, 2-aminoterephthalic acid and DMF are mixed evenly, triethylamine is added, and a reaction is carried out to obtain a zinc organic framework; zinc organic framework, KH560 and toluene are mixed evenly, nitrogen is introduced to replace air, and triethylamine is added while stirring to carry out a reaction to obtain a pretreated organic framework; Step A2: uniformly mixing the pretreated organic framework, acrylic acid, p-toluenesulfonic acid and toluene, introducing nitrogen to replace the air, and reacting to obtain a modified organic framework; uniformly mixing sodium hypophosphite and acetic acid, introducing nitrogen to replace the air, stirring and adding tert-butyl peroxide and concentrated sulfuric acid, heating and adding the modified organic framework, and reacting to obtain a precursor; Step A3: dispersing the precursor in ethanol, introducing nitrogen to remove air, adding aluminum sulfate, and reacting to obtain a modified precursor; The modified precursor is dispersed in ethanol, methyltrimethoxysilane, a modifier, KH570 and tetrabutyl titanate are added, stirred, a hydrochloric acid solution and deionized water are added, reacted, heated and kept, and a modified filler is obtained; The modifier is prepared by the following steps: Step B1: Mix cyanuric chloride, 2,6,7-trioxa-1-phosphabicyclo (2.2.2) octane-4-methanol-1-oxide, triethylamine and tetrahydrofuran, react, add diethanolamine, heat and reflux to react, and obtain intermediate 1; Step B2: Mix the intermediate 1, 4-formylphenylboronic acid, tributyl metaphosphate and toluene for reflux reaction to obtain the intermediate 2; mix the intermediate 2, KH550 and ethanol evenly, introduce nitrogen protection, reflux reaction, add DOPO, continue the reaction, and obtain the modifier.

2. The method for preparing a masterbatch with flame retardant function according to claim 1, characterized in that: The amount ratio of zinc nitrate hexahydrate, 2-aminoterephthalic acid, DMF and triethylamine described in step A1 is 16mmol:8mmol:10mL:1mL, the molar ratio of amino groups on the zinc organic framework and KH560 is 1:2, and the volume ratio of KH560 and toluene is 1:

5.

3. The method for preparing a masterbatch with flame retardant function according to claim 1, characterized in that: The molar ratio of hydroxyl groups and acrylic acid on the pretreated organic framework described in step A2 is 1:1, the amount of p-toluenesulfonic acid is 1% of the mass of acrylic acid, the amount ratio of acrylic acid and toluene is 1g:8mL, the amount ratio of sodium hypophosphite, acetic acid, tert-butyl peroxide, concentrated sulfuric acid and modified organic framework is 15g:25mL:1g:2g:20g, and the mass fraction of concentrated sulfuric acid is 70%.

4. The method for preparing a masterbatch with flame retardant function according to claim 1, characterized in that: The amount ratio of the precursor, ethanol and aluminum sulfate described in step A3 is 3g:10mL:1g, the amount ratio of the modified precursor, ethanol, methyltrimethoxysilane, modifier, KH570, tetrabutyl titanate, hydrochloric acid solution and deionized water is 2g:20mL:4mL:0.5g:2mL:1mL:3mL:5mL, and the mass fraction of the hydrochloric acid solution is 10%.

5. The method for preparing a masterbatch with flame retardant function according to claim 1, characterized in that: The amount ratio of cyanuric chloride, 2,6,7-trioxa-1-phosphabicyclo (2.2.2) octane-4-methanol-1-oxide, triethylamine, tetrahydrofuran and diethanolamine described in step B1 is 1 mmol:2 mmol:3.1 mmol:20 mL:1.2 mmol.

6. The method for preparing a masterbatch with flame retardant function according to claim 1, characterized in that: The amount ratio of intermediate 1, 4-formylphenylboric acid and toluene in step B2 is 1mmol:1mmol:5mL, the amount of tributyl metaphosphate is 1.5% of the mass of 4-formylphenylboronic acid, and the amount ratio of intermediate 2, KH550, ethanol and DOPO is 1mmol:1mmol:15mL:1.2mmol.

7. A masterbatch with flame retardant function, characterized in that: Prepared according to any one of claims 1 to 6.

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