A graphene-based antistatic PPO material and preparation method thereof

Abstract

The invention discloses an antistatic PPO material based on graphene and a preparation method thereof. Aminated polyphenylene ether and a modified filler are reacted to obtain the modified polyphenylene ether, and the modified polyphenylene ether is treated with benzenesulfonyl chloride to obtain the antistatic PPO material. When the aminated polyphenylene ether and the modified filler are reacted, the modified filler is equivalent to a cross-linking agent, so that the molecular chain segments of the aminated polyphenylene ether are cross-linked with each other, and the modified filler is interspersed between the molecular chain segments. The interior of the modified filler is graphene with good conductive effect, so that the material has an antistatic effect, and the surface of the modified filler contains an organosilicon segment. When the material is burned, the phosphorus-containing organosilicon segment on the surface of the modified filler forms a dense carbon layer of P-O-Si, and the nitrogen element of the side chain can generate amino radicals to capture active hydrogen atoms and hydroxyl radicals, thereby interrupting the combustion chain reaction, and the sulfur element can release sulfur dioxide gas to dilute the oxygen concentration, so that the material has a good flame retardant effect.

Description

Technical Field

[0001] The invention relates to the technical field of antistatic material preparation, and in particular to a graphene-based antistatic PPO material and a preparation method thereof. Background Art

[0002] The Chinese name of PPO is polyphenylene ether. It is one of the world's five major general engineering plastics. It has the advantages of high rigidity, high heat resistance, flame retardancy, high strength and excellent electrical properties. In addition, polyphenylene ether also has the advantages of wear resistance, non-toxicity and pollution resistance. The dielectric constant and dielectric loss of PPO are one of the smallest varieties among engineering plastics. It is almost unaffected by temperature and humidity and can be used in low, medium and high frequency electric field fields. However, traditional PPE materials have the disadvantages of strong static electricity accumulation and flammability, which seriously affect its safety and reliability in the above fields. Summary of the invention

[0003] The purpose of the present invention is to provide an antistatic PPO material based on graphene and a preparation method thereof, which solves the problem that the current PPO material has a general antistatic effect and a poor flame retardant effect.

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

[0005] A method for preparing an antistatic PPO material based on graphene specifically comprises the following steps:

[0006] Step A1: p-nitrobenzaldehyde, phenol, zinc chloride, p-toluenesulfonic acid and DMF are mixed evenly, nitrogen is introduced for protection, and the reaction is carried out for 20-25 hours at a speed of 150-200 r / min and a temperature of 45-50° C. to obtain a functional monomer; the functional monomer, 2,6-dimethylphenol, copper chloride, pyridine and DMF are mixed evenly, and the reaction is carried out for 2-3 hours at a speed of 120-150 r / min, a temperature of 35-40° C. and an oxygen atmosphere to obtain a functionalized polyphenylene ether;

[0007] Step A2: zinc powder, hydrochloric acid, deionized water and DMF are mixed, stirred at a speed of 150-200 r / min and a temperature of 80-85° C., and functionalized polyphenylene ether is added, reacted for 1-1.5 hours, and the pH value is adjusted to 7.5-8 to obtain amino polyphenylene ether, and the amino polyphenylene ether, modified filler and DMF are mixed uniformly, stirred at a speed of 120-150 r / min and a temperature of 0-3° C., aluminum chloride is added, and the temperature is raised to 40-50° C., and the reaction is carried out for 6-8 hours to obtain modified polyphenylene ether;

[0008] Step A3: The modified polyphenylene ether, benzenesulfonyl chloride, triethylamine and DMF are mixed evenly, and reacted for 3-5 hours at a rotation speed of 300-500 r / min and a temperature of 30-40° C. to obtain an antistatic PPO material.

[0009] Furthermore, the molar ratio of p-nitrobenzaldehyde, phenol, zinc chloride and p-toluenesulfonic acid in step A1 is 10:22:1:1, and the molar ratio of functional monomer, 2,6-dimethylphenol, copper chloride and pyridine is 1:11:0.12:0.24.

[0010] Furthermore, the dosage ratio of zinc powder, hydrochloric acid, deionized water, DMF and functionalized polyphenylene ether described in step A2 is 2.5g:2g:20mL:50mL:1.5g, the mass ratio of amino polyphenylene ether and modified filler is 10:1, and the dosage of aluminum chloride is 3‰ of the mass of the modified filler.

[0011] Furthermore, the mass ratio of the modified polyphenylene ether, benzenesulfonyl chloride and triethylamine described in step A3 is 20:1:0.6.

[0012] Further, the modified filler is prepared by the following steps:

[0013] Step B1: Graphene oxide, sodium hydroxide, deionized water and bromoacetic acid are mixed, and stirred for 3-5 hours at a speed of 600-800 r / min and a temperature of 25-30° C. to obtain carboxylated graphene; carboxylated graphene, γ-aminopropylmethyldiethoxysilane, dicyclohexylcarbodiimide and toluene are mixed, nitrogen is introduced for protection, and the reaction is carried out for 2-3 hours at a speed of 200-300 r / min and a temperature of 20-25° C. to obtain functionalized graphene;

[0014] Step B2: Dispersing functionalized graphene in toluene, adding hydrazine hydrate, reacting at a speed of 300-500 r / min and a temperature of 90-95° C. for 20-25 h to obtain modified graphene, mixing 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide, p-hydroxystyrene, triethylamine and DMF, introducing nitrogen protection, reacting at a speed of 200-300 r / min and a temperature of 60-70° C. for 20-25 h to obtain a modifier, and uniformly mixing the modifier, dimethylchlorosilane, chloroplatinic acid and DMF, introducing nitrogen protection, reacting at a speed of 200-300 r / min and a temperature of 70-75° C. for 4-6 h to obtain a flame retardant monomer;

[0015] Step B3: octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, flame retardant monomer, modified graphene, tetramethylammonium hydroxide, hexamethyldisiloxane, deionized water and dimethyl sulfoxide are mixed evenly, nitrogen is introduced for protection, and the reaction is carried out for 3-5 hours at a speed of 120-150r / min and a temperature of 105-110°C to obtain a functional filler; the functional filler, allyl alcohol glycidyl ether, chloroplatinic acid and DMF are mixed evenly, nitrogen is introduced for protection, and the reaction is carried out for 4-6 hours at a speed of 200-300r / min and a temperature of 70-75°C to obtain a modified filler.

[0016] Furthermore, the amount ratio of graphene oxide, sodium hydroxide, deionized water and bromoacetic acid described in step B1 is 100 mg: 1 g: 100 mL: 2 g, and the molar ratio of carboxyl groups on carboxylated graphene, γ-aminopropylmethyldiethoxysilane and dicyclohexylcarbodiimide is 1:1:1.2.

[0017] Furthermore, the amount ratio of the functionalized graphene, toluene and hydrazine hydrate described in step B2 is 1g:120mL:10mL, the molar ratio of 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide, p-hydroxystyrene and triethylamine is 1:2:2, the molar ratio of the modifier and dimethylchlorosilane is 1:2, and the amount of chloroplatinic acid is 1‰ of the mass of dimethylchlorosilane.

[0018] Furthermore, the amount ratio of octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, flame retardant monomer, modified graphene, tetramethylammonium hydroxide, deionized water and hexamethyldisiloxane described in step B3 is 10mmol:5mmol:2mmol:1g:10mmol:20mL:15mmol, the molar ratio of Si-H bonds on the functional filler and allyl alcohol glycidyl ether is 1:1, and the amount of chloroplatinic acid is 1‰ of the mass of allyl alcohol glycidyl ether.

[0019] The beneficial effects of the present invention are as follows: the present invention discloses an antistatic PPO material based on graphene, wherein p-nitrobenzaldehyde and phenol are used as raw materials to carry out a nucleophilic substitution reaction to obtain a functional monomer, the functional monomer and 2,6-dimethylphenol are subjected to an oxidative coupling copolymerization reaction to obtain a functionalized polyphenylene ether, the functionalized polyphenylene ether is reduced by zinc powder to reduce the nitro group of the side chain of the functionalized polyphenylene ether to an amino group to obtain an amino polyphenylene ether, the amino polyphenylene ether is reacted with a modified filler to react the amino group of the side chain of the amino polyphenylene ether with the epoxy group on the modified filler to obtain a modified polyphenylene ether, and the modified polyphenylene ether is reacted with an acyl chloride group on benzenesulfonyl chloride with a hydroxyl group on the modified polyphenylene ether under the action of triethylamine to obtain an antistatic PPO material.

[0020] The modified filler is prepared by reacting graphene oxide as a raw material with bromoacetic acid under the action of sodium hydroxide to obtain carboxylated graphene, reacting the carboxylated graphene with γ-aminopropylmethyldiethoxysilane to make the carboxyl group on the carboxylated graphene and the amino group on the γ-aminopropylmethyldiethoxysilane dehydrate to obtain functionalized graphene, reducing the functionalized graphene with hydrazine hydrate to obtain modified graphene, and reacting 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide with p-hydroxystyrene to make 3,9-dichloro-2,4,8,10-tetraoxa-3,9 The P-Cl on the diphosphaspiro[5.5]undecane 3,9-dioxide is reacted with the hydroxyl group on the p-hydroxystyrene to obtain a modifier, the modifier is reacted with dimethylchlorosilane so that the double bond on the modifier reacts with the Si-H bond on the dimethylchlorosilane to obtain a flame retardant monomer, octamethylcyclotetrasiloxane and tetramethylcyclotetrasiloxane are ring-opened and hydrolyzed and condensed with the flame retardant monomer and the siloxane on the surface of the modified graphene, and then capped with hexamethyldisiloxane to obtain a functional filler, and the functional filler is treated with allyl alcohol glycidyl ether so that the Si-H bond on the surface of the functional filler reacts with the double bond on the allyl alcohol glycidyl ether to obtain a modified filler.

[0021] In the case of amino polyphenylene ether and modified filler, the modified filler is equivalent to a cross-linking agent, so that the amino polyphenylene ether molecular segments are cross-linked with each other, and the modified filler is interspersed between the molecular segments. The interior of the modified filler is graphene with a good conductive effect, so that the prepared material has a good antistatic effect, and the surface of the modified filler contains silicone segments, the silicone segments contain phosphorus elements, and the polyphenylene ether molecular segments contain nitrogen and sulfur elements. When the material burns, the phosphorus-containing silicone segments on the surface of the modified filler will form a dense carbon layer of PO-Si, and the nitrogen elements in the side chains can produce amino free radicals, thereby capturing active hydrogen atoms and hydroxyl free radicals, thereby interrupting the combustion chain reaction, and the sulfur element can release sulfur dioxide gas, thereby diluting the oxygen concentration, so that the material has a good flame retardant effect. DETAILED DESCRIPTION

[0022] 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.

[0023] Embodiment 1: A method for preparing an antistatic PPO material based on graphene, comprising the following steps:

[0024] Step A1: p-nitrobenzaldehyde, phenol, zinc chloride, p-toluenesulfonic acid and DMF are mixed evenly, nitrogen is introduced for protection, and the reaction is carried out for 20 hours at a speed of 150 r / min and a temperature of 45° C. to obtain a functional monomer; the functional monomer, 2,6-dimethylphenol, copper chloride, pyridine and DMF are mixed evenly, and the reaction is carried out for 2 hours at a speed of 120 r / min, a temperature of 35° C. and an oxygen atmosphere to obtain a functionalized polyphenylene ether;

[0025] Step A2: zinc powder, hydrochloric acid, deionized water and DMF are mixed, stirred at a speed of 150 r / min and a temperature of 80° C., and functionalized polyphenylene ether is added, reacted for 1 hour, and the pH value is adjusted to 7.5 to obtain amino polyphenylene ether, and the amino polyphenylene ether, modified filler and DMF are mixed uniformly, stirred at a speed of 120 r / min and a temperature of 0° C., aluminum chloride is added, the temperature is raised to 40° C., and the reaction is carried out for 6 hours to obtain modified polyphenylene ether;

[0026] Step A3: The modified polyphenylene ether, benzenesulfonyl chloride, triethylamine and DMF were mixed evenly, and reacted for 3 hours at a rotation speed of 300 r / min and a temperature of 30° C. to obtain an antistatic PPO material.

[0027] The molar ratio of p-nitrobenzaldehyde, phenol, zinc chloride and p-toluenesulfonic acid in step A1 is 10:22:1:1, and the molar ratio of functional monomer, 2,6-dimethylphenol, copper chloride and pyridine is 1:11:0.12:0.24.

[0028] The amount ratio of zinc powder, hydrochloric acid, deionized water, DMF and functionalized polyphenylene ether described in step A2 is 2.5g:2g:20mL:50mL:1.5g, the mass ratio of amino polyphenylene ether and modified filler is 10:1, and the amount of aluminum chloride is 3‰ of the mass of the modified filler.

[0029] The mass ratio of the modified polyphenylene ether, benzenesulfonyl chloride and triethylamine described in step A3 is 20:1:0.6.

[0030] The modified filler is prepared by the following steps:

[0031] Step B1: Graphene oxide, sodium hydroxide, deionized water and bromoacetic acid are mixed, stirred for 3 hours at a speed of 600 r / min and a temperature of 25° C. to obtain carboxylated graphene; carboxylated graphene, γ-aminopropylmethyldiethoxysilane, dicyclohexylcarbodiimide and toluene are mixed, nitrogen is introduced for protection, and the reaction is carried out at a speed of 200 r / min and a temperature of 20° C. for 2 hours to obtain functionalized graphene;

[0032] Step B2: functionalized graphene is dispersed in toluene, hydrazine hydrate is added, and the reaction is carried out at a speed of 300 r / min and a temperature of 90° C. for 20 hours to obtain modified graphene, 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide, p-hydroxystyrene, triethylamine and DMF are mixed, nitrogen is introduced for protection, and the reaction is carried out at a speed of 200 r / min and a temperature of 60° C. for 20 hours to obtain a modifier, and the modifier, dimethylchlorosilane, chloroplatinic acid and DMF are mixed uniformly, nitrogen is introduced for protection, and the reaction is carried out at a speed of 200 r / min and a temperature of 70° C. for 4 hours to obtain a flame retardant monomer;

[0033] Step B3: octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, flame retardant monomer, modified graphene, tetramethylammonium hydroxide, hexamethyldisiloxane, deionized water and dimethyl sulfoxide are mixed evenly, nitrogen is introduced for protection, and the reaction is carried out for 3 hours at a speed of 120 r / min and a temperature of 105°C to obtain a functional filler; the functional filler, allyl alcohol glycidyl ether, chloroplatinic acid and DMF are mixed evenly, nitrogen is introduced for protection, and the reaction is carried out for 4 hours at a speed of 200 r / min and a temperature of 70°C to obtain a modified filler.

[0034] The amount ratio of graphene oxide, sodium hydroxide, deionized water and bromoacetic acid described in step B1 is 100 mg: 1 g: 100 mL: 2 g, and the molar ratio of carboxyl groups on carboxylated graphene, γ-aminopropylmethyldiethoxysilane and dicyclohexylcarbodiimide is 1: 1: 1.2.

[0035] The amount ratio of the functionalized graphene, toluene and hydrazine hydrate described in step B2 is 1g:120mL:10mL, the molar ratio of 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide, p-hydroxystyrene and triethylamine is 1:2:2, the molar ratio of the modifier and dimethylchlorosilane is 1:2, and the amount of chloroplatinic acid is 1‰ of the mass of dimethylchlorosilane.

[0036] The amount ratio of octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, flame retardant monomer, modified graphene, tetramethylammonium hydroxide, deionized water and hexamethyldisiloxane described in step B3 is 10mmol:5mmol:2mmol:1g:10mmol:20mL:15mmol, the molar ratio of Si-H bonds on the functional filler and allyl alcohol glycidyl ether is 1:1, and the amount of chloroplatinic acid is 1‰ of the mass of allyl alcohol glycidyl ether.

[0037] Embodiment 2: A method for preparing an antistatic PPO material based on graphene, comprising the following steps:

[0038] Step A1: p-nitrobenzaldehyde, phenol, zinc chloride, p-toluenesulfonic acid and DMF are mixed evenly, nitrogen is introduced for protection, and the reaction is carried out for 20 hours at a speed of 150 r / min and a temperature of 50° C. to obtain a functional monomer; the functional monomer, 2,6-dimethylphenol, copper chloride, pyridine and DMF are mixed evenly, and the reaction is carried out for 2 hours at a speed of 120 r / min, a temperature of 40° C. and an oxygen atmosphere to obtain a functionalized polyphenylene ether;

[0039] Step A2: zinc powder, hydrochloric acid, deionized water and DMF are mixed, and the functionalized polyphenylene ether is added under the conditions of a rotation speed of 200 r / min and a temperature of 80°C, and the reaction is carried out for 1.5 hours, and the pH value is adjusted to 7.5 to obtain amino polyphenylene ether, and the amino polyphenylene ether, modified filler and DMF are mixed uniformly, and aluminum chloride is added under the conditions of a rotation speed of 150 r / min and a temperature of 0°C, and the temperature is raised to 45°C, and the reaction is carried out for 7 hours to obtain modified polyphenylene ether;

[0040] Step A3: The modified polyphenylene ether, benzenesulfonyl chloride, triethylamine and DMF were mixed evenly, and reacted at a speed of 300 r / min and a temperature of 35° C. for 4 hours to obtain an antistatic PPO material.

[0041] The molar ratio of p-nitrobenzaldehyde, phenol, zinc chloride and p-toluenesulfonic acid in step A1 is 10:22:1:1, and the molar ratio of functional monomer, 2,6-dimethylphenol, copper chloride and pyridine is 1:11:0.12:0.24.

[0042] The amount ratio of zinc powder, hydrochloric acid, deionized water, DMF and functionalized polyphenylene ether described in step A2 is 2.5g:2g:20mL:50mL:1.5g, the mass ratio of amino polyphenylene ether and modified filler is 10:1, and the amount of aluminum chloride is 3‰ of the mass of the modified filler.

[0043] The mass ratio of the modified polyphenylene ether, benzenesulfonyl chloride and triethylamine described in step A3 is 20:1:0.6.

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

[0045] Step B1: Graphene oxide, sodium hydroxide, deionized water and bromoacetic acid are mixed, stirred for 4 hours at a speed of 800 r / min and a temperature of 25° C. to obtain carboxylated graphene; carboxylated graphene, γ-aminopropylmethyldiethoxysilane, dicyclohexylcarbodiimide and toluene are mixed, nitrogen is introduced for protection, and the reaction is carried out at a speed of 200 r / min and a temperature of 25° C. for 2 hours to obtain functionalized graphene;

[0046] Step B2: functionalized graphene is dispersed in toluene, hydrazine hydrate is added, and the reaction is carried out for 20 hours at a speed of 500 r / min and a temperature of 90° C. to obtain modified graphene, 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide, p-hydroxystyrene, triethylamine and DMF are mixed, nitrogen is introduced for protection, and the reaction is carried out for 20 hours at a speed of 300 r / min and a temperature of 65° C. to obtain a modifier, and the modifier, dimethylchlorosilane, chloroplatinic acid and DMF are mixed uniformly, nitrogen is introduced for protection, and the reaction is carried out for 5 hours at a speed of 200 r / min and a temperature of 75° C. to obtain a flame retardant monomer;

[0047] Step B3: octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, flame retardant monomer, modified graphene, tetramethylammonium hydroxide, hexamethyldisiloxane, deionized water and dimethyl sulfoxide are mixed evenly, nitrogen is introduced for protection, and the reaction is carried out for 4 hours at a speed of 120 r / min and a temperature of 110°C to obtain a functional filler; the functional filler, allyl alcohol glycidyl ether, chloroplatinic acid and DMF are mixed evenly, nitrogen is introduced for protection, and the reaction is carried out for 5 hours at a speed of 200 r / min and a temperature of 75°C to obtain a modified filler.

[0048] The amount ratio of graphene oxide, sodium hydroxide, deionized water and bromoacetic acid described in step B1 is 100 mg: 1 g: 100 mL: 2 g, and the molar ratio of carboxyl groups on carboxylated graphene, γ-aminopropylmethyldiethoxysilane and dicyclohexylcarbodiimide is 1: 1: 1.2.

[0049] The amount ratio of the functionalized graphene, toluene and hydrazine hydrate described in step B2 is 1g:120mL:10mL, the molar ratio of 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide, p-hydroxystyrene and triethylamine is 1:2:2, the molar ratio of the modifier and dimethylchlorosilane is 1:2, and the amount of chloroplatinic acid is 1‰ of the mass of dimethylchlorosilane.

[0050] The amount ratio of octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, flame retardant monomer, modified graphene, tetramethylammonium hydroxide, deionized water and hexamethyldisiloxane described in step B3 is 10mmol:5mmol:2mmol:1g:10mmol:20mL:15mmol, the molar ratio of Si-H bonds on the functional filler and allyl alcohol glycidyl ether is 1:1, and the amount of chloroplatinic acid is 1‰ of the mass of allyl alcohol glycidyl ether.

[0051] Embodiment 3: A method for preparing an antistatic PPO material based on graphene, comprising the following steps:

[0052] Step A1: p-nitrobenzaldehyde, phenol, zinc chloride, p-toluenesulfonic acid and DMF are mixed evenly, nitrogen is introduced for protection, and the reaction is carried out for 25 hours at a speed of 200 r / min and a temperature of 50° C. to obtain a functional monomer; the functional monomer, 2,6-dimethylphenol, copper chloride, pyridine and DMF are mixed evenly, and the reaction is carried out for 3 hours at a speed of 150 r / min, a temperature of 40° C. and an oxygen atmosphere to obtain a functionalized polyphenylene ether;

[0053] Step A2: zinc powder, hydrochloric acid, deionized water and DMF are mixed, and the functionalized polyphenylene ether is added under the conditions of a rotation speed of 200 r / min and a temperature of 85° C., and the reaction is carried out for 1.5 hours, and the pH value is adjusted to 8 to obtain an amino polyphenylene ether, and the amino polyphenylene ether, modified filler and DMF are mixed uniformly, and aluminum chloride is added under the conditions of a rotation speed of 150 r / min and a temperature of 3° C., and the temperature is raised to 50° C. and the reaction is carried out for 8 hours to obtain a modified polyphenylene ether;

[0054] Step A3: The modified polyphenylene ether, benzenesulfonyl chloride, triethylamine and DMF were mixed evenly, and reacted for 5 hours at a rotation speed of 500 r / min and a temperature of 40° C. to obtain an antistatic PPO material.

[0055] The molar ratio of p-nitrobenzaldehyde, phenol, zinc chloride and p-toluenesulfonic acid in step A1 is 10:22:1:1, and the molar ratio of functional monomer, 2,6-dimethylphenol, copper chloride and pyridine is 1:11:0.12:0.24.

[0056] The amount ratio of zinc powder, hydrochloric acid, deionized water, DMF and functionalized polyphenylene ether described in step A2 is 2.5g:2g:20mL:50mL:1.5g, the mass ratio of amino polyphenylene ether and modified filler is 10:1, and the amount of aluminum chloride is 3‰ of the mass of the modified filler.

[0057] The mass ratio of the modified polyphenylene ether, benzenesulfonyl chloride and triethylamine described in step A3 is 20:1:0.6.

[0058] The modified filler is prepared by the following steps:

[0059] Step B1: Graphene oxide, sodium hydroxide, deionized water and bromoacetic acid are mixed, stirred for 5 hours at a speed of 800 r / min and a temperature of 30° C. to obtain carboxylated graphene; carboxylated graphene, γ-aminopropylmethyldiethoxysilane, dicyclohexylcarbodiimide and toluene are mixed, nitrogen is introduced for protection, and the reaction is carried out for 3 hours at a speed of 300 r / min and a temperature of 25° C. to obtain functionalized graphene;

[0060] Step B2: functionalized graphene is dispersed in toluene, hydrazine hydrate is added, and the reaction is carried out for 25 hours at a speed of 500 r / min and a temperature of 95° C. to obtain modified graphene; 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide, p-hydroxystyrene, triethylamine and DMF are mixed, nitrogen is introduced for protection, and the reaction is carried out for 25 hours at a speed of 300 r / min and a temperature of 70° C. to obtain a modifier; the modifier, dimethylchlorosilane, chloroplatinic acid and DMF are mixed evenly, nitrogen is introduced for protection, and the reaction is carried out for 6 hours at a speed of 300 r / min and a temperature of 75° C. to obtain a flame retardant monomer;

[0061] Step B3: octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, flame retardant monomer, modified graphene, tetramethylammonium hydroxide, hexamethyldisiloxane, deionized water and dimethyl sulfoxide are mixed evenly, nitrogen is introduced for protection, and the reaction is carried out for 5 hours at a speed of 150 r / min and a temperature of 110°C to obtain a functional filler; the functional filler, allyl alcohol glycidyl ether, chloroplatinic acid and DMF are mixed evenly, nitrogen is introduced for protection, and the reaction is carried out for 6 hours at a speed of 300 r / min and a temperature of 75°C to obtain a modified filler.

[0062] The amount ratio of graphene oxide, sodium hydroxide, deionized water and bromoacetic acid described in step B1 is 100 mg: 1 g: 100 mL: 2 g, and the molar ratio of carboxyl groups on carboxylated graphene, γ-aminopropylmethyldiethoxysilane and dicyclohexylcarbodiimide is 1: 1: 1.2.

[0063] The amount ratio of the functionalized graphene, toluene and hydrazine hydrate described in step B2 is 1g:120mL:10mL, the molar ratio of 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide, p-hydroxystyrene and triethylamine is 1:2:2, the molar ratio of the modifier and dimethylchlorosilane is 1:2, and the amount of chloroplatinic acid is 1‰ of the mass of dimethylchlorosilane.

[0064] The amount ratio of octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, flame retardant monomer, modified graphene, tetramethylammonium hydroxide, deionized water and hexamethyldisiloxane described in step B3 is 10mmol:5mmol:2mmol:1g:10mmol:20mL:15mmol, the molar ratio of Si-H bonds on the functional filler and allyl alcohol glycidyl ether is 1:1, and the amount of chloroplatinic acid is 1‰ of the mass of allyl alcohol glycidyl ether.

[0065] Comparative Example 1: Compared with Example 1, this comparative example uses modified polyphenylene ether instead of antistatic PPO material, and the remaining steps are the same.

[0066] Comparative Example 2: Compared with Example 1, octamethylcyclotetrasiloxane, flame retardant monomer, modified graphene, tetramethylammonium hydroxide, hexamethyldisiloxane, deionized water and dimethyl sulfoxide are uniformly mixed, nitrogen is introduced for protection, and the reaction is carried out at a speed of 120 r / min and a temperature of 105°C for 3 hours. The obtained product replaces the modified filler, and the other steps are the same.

[0067] Comparative Example 3: Compared with Example 1, no flame retardant monomer was added in this comparative example, and the remaining steps were the same.

[0068] The materials obtained in Examples 1-3 and Comparative Examples 1-3 were made into 125mm×13mm×10mm specimens according to the standard of GB / T2408-2008, and the vertical burning level was tested. The materials obtained in Examples 1-3 and Comparative Examples 1-3 were made into 130mm×10mm×10mm specimens according to the standard of GB / T2406.2-2009, and the limiting oxygen index was tested. The test results are described in Table 1 below.

[0069] Table 1

[0070]

[0071] It can be seen from Table 1 above that the present invention has a very good flame retardant effect.

[0072] 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 an antistatic PPO material based on graphene, characterized in that: The specific steps include: Step A1: p-nitrobenzaldehyde, phenol, zinc chloride, p-toluenesulfonic acid and DMF are uniformly mixed, nitrogen is introduced for protection, and a reaction is carried out to obtain a functional monomer; the functional monomer, 2,6-dimethylphenol, copper chloride, pyridine and DMF are mixed for reaction to obtain a functionalized polyphenylene ether; Step A2: zinc powder, hydrochloric acid, deionized water and DMF are mixed, stirred and functionalized polyphenylene ether is added, and after reaction, the pH is adjusted to be alkaline to obtain amino polyphenylene ether, the amino polyphenylene ether, modified filler and DMF are mixed and stirred, aluminum chloride is added, and the temperature is raised to react to obtain modified polyphenylene ether; Step A3: mixing modified polyphenylene ether, benzenesulfonyl chloride, triethylamine and DMF to obtain an antistatic PPO material; The modified filler is prepared by the following steps: Step B1: mixing graphene oxide, sodium hydroxide, deionized water and bromoacetic acid to obtain carboxylated graphene, mixing carboxylated graphene, γ-aminopropylmethyldiethoxysilane, dicyclohexylcarbodiimide and toluene, introducing nitrogen protection, and reacting to obtain functionalized graphene; Step B2: dispersing functionalized graphene in toluene, adding hydrazine hydrate, reacting to obtain modified graphene, mixing 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide, p-hydroxystyrene, triethylamine and DMF, introducing nitrogen protection, reacting to obtain a modifier, and uniformly mixing the modifier, dimethylchlorosilane, chloroplatinic acid and DMF, introducing nitrogen protection, reacting to obtain a flame retardant monomer; Step B3: octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, flame retardant monomer, modified graphene, tetramethylammonium hydroxide, hexamethyldisiloxane, deionized water and dimethyl sulfoxide are mixed evenly, nitrogen is introduced to protect, and a reaction is carried out to obtain a functional filler; the functional filler, allyl alcohol glycidyl ether, chloroplatinic acid and DMF are mixed evenly, nitrogen is introduced to protect, and a reaction is carried out to obtain a modified filler.

2. The method for preparing a graphene-based antistatic PPO material according to claim 1, characterized in that: The molar ratio of p-nitrobenzaldehyde, phenol, zinc chloride and p-toluenesulfonic acid in step A1 is 10:22:1:1, and the molar ratio of functional monomer, 2,6-dimethylphenol, copper chloride and pyridine is 1:11:0.12:0.

24.

3. The method for preparing a graphene-based antistatic PPO material according to claim 1, characterized in that: The amount ratio of zinc powder, hydrochloric acid, deionized water, DMF and functionalized polyphenylene ether described in step A2 is 2.5g:2g:20mL:50mL:1.5g, and the mass ratio of amino polyphenylene ether and modified filler is 10:

1.

4. The method for preparing a graphene-based antistatic PPO material according to claim 1, characterized in that: The mass ratio of the modified polyphenylene ether, benzenesulfonyl chloride and triethylamine described in step A3 is 20:1:0.

6.

5. The method for preparing a graphene-based antistatic PPO material according to claim 1, characterized in that: The amount ratio of graphene oxide, sodium hydroxide, deionized water and bromoacetic acid described in step B1 is 100 mg: 1 g: 100 mL: 2 g, and the molar ratio of carboxyl groups on carboxylated graphene, γ-aminopropylmethyldiethoxysilane and dicyclohexylcarbodiimide is 1: 1: 1.

2.

6. The method for preparing a graphene-based antistatic PPO material according to claim 1, characterized in that: The amount ratio of the functionalized graphene, toluene and hydrazine hydrate described in step B2 is 1g:120mL:10mL, the molar ratio of 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide, p-hydroxystyrene and triethylamine is 1:2:2, and the molar ratio of the modifier and dimethylchlorosilane is 1:

2.

7. The method for preparing a graphene-based antistatic PPO material according to claim 1, characterized in that: The amount ratio of octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, flame retardant monomer, modified graphene, tetramethylammonium hydroxide, deionized water and hexamethyldisiloxane described in step B3 is 10mmol:5mmol:2mmol:1g:10mmol:20mL:15mmol, and the molar ratio of Si-H bonds on the functional filler and allyl alcohol glycidyl ether is 1:

1.

8. An antistatic PPO material based on graphene, characterized in that: Prepared according to any one of claims 1 to 7.

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