An CNT-based antistatic MPPE composite material and its preparation method

Abstract

The present invention discloses an antistatic MPPE composite based on CNT and a preparation method thereof. The composite material comprises the following raw materials in parts by weight: 40-50 parts of modified polyphenylene ether, 40-50 parts of modified polystyrene, 10-15 parts of modified carbon nanotubes, and 1-1.5 parts of zinc oxide. Modified carbon nanotubes are added to the composite filler. The modified carbon nanotubes have a good conductive effect, thereby enabling the composite material to form a conductive path and increasing its antistatic effect. When the modified polyphenylene ether, modified polystyrene, modified carbon nanotubes, and zinc oxide are melt-blended, under the action of zinc oxide, the composite of the modified polyphenylene ether and the modified polystyrene can undergo a DA reaction with maleimide on the modified carbon nanotubes to form a dynamic crosslinking. The dynamic crosslinking can absorb and disperse energy when the composite material is impacted, and enable the molecular chain segments to undergo greater movement when impacted, thereby helping the material to deform without breaking.

Description

Technical Field

[0001] The present invention relates to the technical field of the preparation of MPPE composites, and particularly relates to an antistatic MPPE composite based on CNT and a preparation method thereof. Background Art

[0002] Modified polyphenylene ether (MPPE) is mainly obtained by blending polyphenylene ether and polystyrene. Due to the presence of benzene rings in polyphenylene ether, the potential barrier for intramolecular rotation of the molecular chain segments increases, the molecular chain is a rigid chain, there are no hydrolyzable groups or polar groups, and the structure is relatively regular and symmetric, so that polyphenylene ether has excellent heat resistance, hydrolysis stability, low moisture absorption rate, excellent dielectric properties and a relatively high glass transition temperature, and is widely used in various industries. However, polyphenylene ether itself also has disadvantages, such as poor electrical conductivity, easy generation of static electricity during long-term use, and poor impact toughness, easy brittle fracture, which affects the use of modified polyphenylene ether. Carbon nanotubes (CNT) are a common additive to increase the antistatic property of modified polyphenylene ether, but the simple melt blending effect is not good, resulting in poor antistatic effect of the prepared modified polyphenylene ether, thus affecting the normal use. Summary of the Invention

[0003] The purpose of the present invention is to provide an antistatic MPPE composite based on CNT and a preparation method thereof, which solves the problems of unstable antistatic effect and poor toughness of the MPPE composite at the present stage.

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

[0005] A preparation method of an antistatic MPPE composite based on CNT specifically includes the following steps:

[0006] Step A1: Mix functionalized polyphenylene ether, furan carbonyl chloride, 4-dimethylaminopyridine, triethylamine and ethylene glycol dimethyl ether, and react for 1 - 1.5 h under the conditions of a rotation speed of 200 - 300 r / min and a temperature of 0 °C to obtain modified polyphenylene ether. Mix styrene, 4,4'-azobis(4-cyanopentanol) and toluene evenly, introduce nitrogen protection, and react for 10 - 12 h under the conditions of a rotation speed of 120 - 150 r / min and a temperature of 70 - 75 °C to obtain hydroxylated polystyrene;

[0007] Step A2: Mix hydroxylated polystyrene, furan carbonyl chloride, 4-dimethylaminopyridine, triethylamine, and DMF, and react for 2 - 3 h under the conditions of a rotation speed of 200 - 300 r / min and a temperature of 0 °C to obtain modified polystyrene. Disperse carbon nanotubes in ethanol, stir and add KH550 and deionized water under the conditions of a rotation speed of 200 - 300 r / min and a temperature of 60 - 70 °C, and react for 2 - 3 h to obtain amino-functionalized carbon nanotubes;

[0008] Step A3: Mix the amino-functionalized carbon nanotubes, maleic anhydride, triethylamine, and toluene evenly, and reflux and react for 2 - 3 h under the conditions of a rotation speed of 60 - 80 r / min and a temperature of 115 - 120 °C to obtain modified carbon nanotubes. Weigh the following raw materials in parts by weight: 40 - 50 parts of modified polyphenylene ether, 40 - 50 parts of modified polystyrene, 10 - 15 parts of modified carbon nanotubes, and 1 - 1.5 parts of zinc oxide. Extrude and granulate the raw materials under the conditions of a temperature of 230 - 240 °C to obtain a CNT-based antistatic MPPE composite material.

[0009] Furthermore, the dosage ratio of the functionalized polyphenylene ether, furan carbonyl chloride, 4-dimethylaminopyridine, triethylamine, and ethylene glycol dimethyl ether in Step A1 is 1 g:2 g:0.7 g:1 mL:50 mL, and the mass ratio of styrene, 4,4'-azobis(4-cyanopentanol), and toluene is 20:1.2:20.

[0010] Furthermore, the dosage ratio of the hydroxylated polystyrene, furan carbonyl chloride, 4-dimethylaminopyridine, triethylamine, and DMF in Step A2 is 1 g:1.8 g:0.7 g:1 mL:50 mL, and the dosage of KH550 is 2% of the mass of the carbon nanotubes.

[0011] Furthermore, the dosage ratio of the amino-functionalized carbon nanotubes, maleic anhydride, triethylamine, and toluene in Step A3 is 1 g:50 mmol:150 mmol:30 mL.

[0012] Furthermore, the functionalized polyphenylene ether is prepared by the following steps:

[0013] Step B1: Mix sodium hydroxide, isopropanol, and methanol evenly, stir for 3 - 5 h under the conditions of a rotation speed of 120 - 150 r / min and a temperature of 50 - 60 °C, then add 1,3-divinyltetramethyldisiloxane and toluene, and continue to react for 30 - 40 min to obtain an intermediate. Mix the intermediate, pentaerythritol tetrakis(mercaptoacetate), benzophenone, and DMF evenly, and react for 1 - 1.5 h under the conditions of a rotation speed of 60 - 80 r / min and 365 nm ultraviolet light irradiation to obtain a starting monomer;

[0014] Step B2: Mix octamethylcyclotetrasiloxane and concentrated sulfuric acid evenly, and carry out the reaction for 3 - 5 h under the conditions of a rotation speed of 120 - 150 r / min and a temperature of 75 - 80 °C to obtain a chain extender monomer. Mix the starting monomer, the chain extender monomer and DMF, and carry out the reaction for 10 - 15 h under the conditions of a rotation speed of 150 - 200 r / min and a temperature of 60 - 65 °C, then cool down to 10 - 15 °C, add dimethylchlorosilane, and continue the reaction for 10 - 15 h to obtain a modified monomer;

[0015] Step B3: Mix the modified monomer, 4 - vinylphenol, chloroplatinic acid and DMF evenly, and carry out the reaction for 2 - 3 h under the conditions of a rotation speed of 200 - 300 r / min and a temperature of 70 - 80 °C to obtain a functional monomer. Mix the functional monomer, 2,6 - dimethylphenol, copper chloride, pyridine and DMF evenly, and carry out the reaction for 2 - 3 h under the conditions of a rotation speed of 120 - 150 r / min, a temperature of 25 - 30 °C and an oxygen atmosphere to obtain a functionalized polyphenylene ether.

[0016] Furthermore, the dosage ratio of sodium hydroxide, isopropanol, methanol and 1,3 - divinyltetramethyldisiloxane described in Step B1 is 200 mmol: 35 mL: 35 mL: 100 mmol, the molar ratio of the intermediate and pentaerythritol tetrakis(mercaptoacetate) is 4:1, and the dosage of benzophenone is 1% of the mass of the intermediate.

[0017] Furthermore, the dosage of concentrated sulfuric acid described in Step B2 is 1.5% of the mass of octamethylcyclotetrasiloxane, and the molar ratio of the starting monomer, the chain extender monomer and dimethylchlorosilane is 1:4:4.2.

[0018] Furthermore, the molar ratio of the modified monomer and 4 - vinylphenol described in Step B3 is 1:4, and the dosage ratio of the functional monomer, 2,6 - dimethylphenol, copper chloride, pyridine and DMF is 1 g: 20 g: 0.6 g: 50 mL: 200 mL.

[0019] An antistatic MPPE composite based on CNT is prepared by the above - mentioned preparation method.

[0020] Advantages of the present invention: An antistatic MPPE composite based on CNT disclosed by the present invention comprises the following raw materials: modified polyphenylene ether, modified polystyrene, modified carbon nanotubes, and zinc oxide. The modified polyphenylene ether is prepared by reacting functionalized polyphenylene ether and furan carbonyl chloride with 4-dimethylaminopyridine as the catalyst and triethylamine as the acid-binding agent, such that the phenolic hydroxyl group on the modified polyphenylene ether reacts with the acyl chloride on the furan carbonyl chloride. The modified polystyrene is prepared by free radical polymerization of styrene and 4,4'-azobis(4-cyanopentanol) to obtain hydroxylated polystyrene, and then reacting the hydroxylated polystyrene with furan carbonyl chloride, such that the hydroxyl group on the hydroxylated polystyrene reacts with the acyl chloride on the furan carbonyl chloride to obtain modified polystyrene. The carbon nanotubes are treated with KH550 to graft amino groups on the surface to obtain amino-functionalized carbon nanotubes, and then the amino-functionalized carbon nanotubes are reacted with maleic anhydride to form maleimide on the surface of the carbon nanotubes to obtain modified carbon nanotubes.

[0021] The functionalized polyphenylene ether is prepared by reacting 1,3-divinyltetramethyldisiloxane and sodium hydroxide to form a sodium silanol structure to obtain an intermediate, and then subjecting the intermediate and pentaerythritol tetrakis(mercaptoacetate) to a photochemical reaction, such that the double bond on the intermediate reacts with the mercapto group on the pentaerythritol tetrakis(mercaptoacetate) to obtain a starting monomer. Octamethylcyclotetrasiloxane is subjected to ring-opening polymerization using concentrated sulfuric acid as the catalyst to obtain a chain extender monomer. After reacting the starting monomer and the chain extender monomer, it is capped with dimethylchlorosilane to obtain a modified monomer. The modified monomer is reacted with 4-vinylphenol, such that the Si-H bond on the modified monomer reacts with the double bond on the 4-vinylphenol to obtain a functional monomer. The functional monomer is subjected to an oxidative coupling reaction with 2,6-dimethylphenol to obtain the functionalized polyphenylene ether.

[0022] The modified carbon nanotubes are added to the composite filler. The modified carbon nanotubes have good electrical conductivity, thereby enabling the composite material to form a conductive path and increasing its antistatic effect. When the modified polyphenylene ether, modified polystyrene, modified carbon nanotubes, and zinc oxide are melt-blended, under the action of zinc oxide, the composite of the modified polyphenylene ether and the modified polystyrene can undergo a DA reaction with the maleimide on the modified carbon nanotubes to form dynamic crosslinks in the composite material. The dynamic crosslinks can absorb and disperse energy when the composite material is impacted, and enable the molecular chain segments to undergo greater movement when impacted, thereby helping the material to deform without breaking, and greatly improving the impact resistance of the material. The star-shaped structure of the modified polyphenylene ether and the chain-like structure of the modified polystyrene are combined to form a semi-interpenetrating network structure, greatly improving the mechanical properties of the composite material. Detailed implementation manners

[0023] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0024] Embodiment 1. A preparation method of an antistatic MPPE composite based on CNT specifically includes the following steps:

[0025] Step A1: Mix functionalized polyphenylene ether, furan carbonyl chloride, 4-dimethylaminopyridine, triethylamine and ethylene glycol dimethyl ether, and carry out a reaction for 1 h under the conditions of a rotation speed of 200 r / min and a temperature of 0 °C to obtain modified polyphenylene ether. Mix styrene, 4,4'-azobis(4-cyanopentanol) and toluene evenly, introduce nitrogen protection, and carry out a reaction for 10 h under the conditions of a rotation speed of 120 r / min and a temperature of 70 °C to obtain hydroxylated polystyrene;

[0026] Step A2: Mix hydroxylated polystyrene, furan carbonyl chloride, 4-dimethylaminopyridine, triethylamine and DMF, and carry out a reaction for 2 h under the conditions of a rotation speed of 200 r / min and a temperature of 0 °C to obtain modified polystyrene. Disperse carbon nanotubes in ethanol, stir and add KH550 and deionized water under the conditions of a rotation speed of 200 r / min and a temperature of 60 °C, and carry out a reaction for 2 h to obtain amino-functionalized carbon nanotubes;

[0027] Step A3: Mix amino-functionalized carbon nanotubes, maleic anhydride, triethylamine and toluene evenly, and carry out a reflux reaction for 2 h under the conditions of a rotation speed of 60 r / min and a temperature of 115 °C to obtain modified carbon nanotubes. Weigh the following raw materials in parts by weight: 40 parts of modified polyphenylene ether, 40 parts of modified polystyrene, 10 parts of modified carbon nanotubes and 1 part of zinc oxide. Extrude and granulate the raw materials under the condition of a temperature of 230 °C to obtain an antistatic MPPE composite based on CNT.

[0028] The dosage ratio of the functionalized polyphenylene ether, furan carbonyl chloride, 4-dimethylaminopyridine, triethylamine and ethylene glycol dimethyl ether described in Step A1 is 1 g: 2 g: 0.7 g: 1 mL: 50 mL, and the mass ratio of styrene, 4,4'-azobis(4-cyanopentanol) and toluene is 20: 1.2: 20.

[0029] The dosage ratio of the hydroxylated polystyrene, furan carbonyl chloride, 4-dimethylaminopyridine, triethylamine and DMF described in Step A2 is 1 g: 1.8 g: 0.7 g: 1 mL: 50 mL, and the dosage of KH550 is 2% of the mass of the carbon nanotubes.

[0030] The dosage ratio of the aminated carbon nanotubes, maleic anhydride, triethylamine and toluene described in step A3 is 1 g: 50 mmol: 150 mmol: 30 mL.

[0031] The functionalized polyphenylene ether described above is prepared by the following steps:

[0032] Step B1: Mix sodium hydroxide, isopropanol and methanol evenly. Under the conditions of a rotation speed of 120 r / min and a temperature of 50 °C, after stirring for 3 h, add 1,3-divinyltetramethyldisiloxane and toluene, and continue to react for 30 min to obtain an intermediate. Mix the intermediate, pentaerythritol tetrakis(mercaptoacetate), benzophenone and DMF evenly, and under the conditions of a rotation speed of 60 r / min and irradiation with 365 nm ultraviolet light, react for 1 h to obtain a starting monomer;

[0033] Step B2: Mix octamethylcyclotetrasiloxane and concentrated sulfuric acid evenly. Under the conditions of a rotation speed of 120 r / min and a temperature of 75 °C, react for 3 h to obtain a chain extender monomer. Mix the starting monomer, the chain extender monomer and DMF, and under the conditions of a rotation speed of 150 r / min and a temperature of 60 °C, react for 10 h, then cool down to 10 °C, add dimethylchlorosilane, and continue to react for 10 h to obtain a modified monomer;

[0034] Step B3: Mix the modified monomer, 4-vinylphenol, chloroplatinic acid and DMF evenly. Under the conditions of a rotation speed of 200 r / min and a temperature of 70 °C, react for 2 h to obtain a functional monomer. Mix the functional monomer, 2,6-dimethylphenol, copper chloride, pyridine and DMF evenly, and under the conditions of a rotation speed of 120 r / min, a temperature of 25 °C and an oxygen atmosphere, react for 2 h to obtain the functionalized polyphenylene ether.

[0035] The dosage ratio of the sodium hydroxide, isopropanol, methanol and 1,3-divinyltetramethyldisiloxane described in step B1 is 200 mmol: 35 mL: 35 mL: 100 mmol, the molar ratio of the intermediate to pentaerythritol tetrakis(mercaptoacetate) is 4:1, and the dosage of benzophenone is 1% of the mass of the intermediate.

[0036] The dosage of the concentrated sulfuric acid described in step B2 is 1.5% of the mass of octamethylcyclotetrasiloxane, and the molar ratio of the starting monomer, the chain extender monomer and dimethylchlorosilane is 1:4:4.2.

[0037] The molar ratio of the modified monomer to 4-vinylphenol described in step B3 is 1:4, and the dosage ratio of the functional monomer, 2,6-dimethylphenol, copper chloride, pyridine and DMF is 1 g: 20 g: 0.6 g: 50 mL: 200 mL.

[0038] Example 2. A preparation method of an antistatic MPPE composite based on CNT, specifically comprising the following steps:

[0039] Step A1: Mix functionalized polyphenylene ether, furan carbonyl chloride, 4-dimethylaminopyridine, triethylamine, and ethylene glycol dimethyl ether, and react for 1.5 h under the conditions of a rotation speed of 200 r / min and a temperature of 0 °C to obtain modified polyphenylene ether. Mix styrene, 4,4'-azobis(4-cyanopentanol), and toluene evenly, introduce nitrogen protection, and react for 12 h under the conditions of a rotation speed of 120 r / min and a temperature of 70 °C to obtain hydroxylated polystyrene;

[0040] Step A2: Mix hydroxylated polystyrene, furan carbonyl chloride, 4-dimethylaminopyridine, triethylamine, and DMF, and react for 3 h under the conditions of a rotation speed of 200 r / min and a temperature of 0 °C to obtain modified polystyrene. Disperse carbon nanotubes in ethanol, stir and add KH550 and deionized water under the conditions of a rotation speed of 200 r / min and a temperature of 65 °C, and react for 2 h to obtain amino-functionalized carbon nanotubes;

[0041] Step A3: Mix amino-functionalized carbon nanotubes, maleic anhydride, triethylamine, and toluene evenly, and reflux and react for 3 h under the conditions of a rotation speed of 80 r / min and a temperature of 115 °C to obtain modified carbon nanotubes. Weigh the following raw materials in parts by weight: 40 parts of modified polyphenylene ether, 50 parts of modified polystyrene, 13 parts of modified carbon nanotubes, and 1.3 parts of zinc oxide. Extrude and pelletize the raw materials under the condition of a temperature of 235 °C to obtain an antistatic MPPE composite based on CNT.

[0042] The dosage ratio of the functionalized polyphenylene ether, furan carbonyl chloride, 4-dimethylaminopyridine, triethylamine, and ethylene glycol dimethyl ether described in Step A1 is 1 g:2 g:0.7 g:1 mL:50 mL, and the mass ratio of styrene, 4,4'-azobis(4-cyanopentanol), and toluene is 20:1.2:20.

[0043] The dosage ratio of the hydroxylated polystyrene, furan carbonyl chloride, 4-dimethylaminopyridine, triethylamine, and DMF described in Step A2 is 1 g:1.8 g:0.7 g:1 mL:50 mL, and the dosage of KH550 is 2% of the mass of the carbon nanotubes.

[0044] The dosage ratio of the amino-functionalized carbon nanotubes, maleic anhydride, triethylamine, and toluene described in Step A3 is 1 g:50 mmol:150 mmol:30 mL.

[0045] The functionalized polyphenylene ether is prepared by the following steps:

[0046] Step B1: Mix sodium hydroxide, isopropanol, and methanol evenly. Under the conditions of a rotation speed of 150 r / min and a temperature of 55 °C, stir for 4 h, then add 1,3-divinyltetramethyldisiloxane and toluene, and continue the reaction for 35 min to obtain an intermediate. Mix the intermediate, pentaerythritol tetrakis(mercaptoacetate), benzophenone, and DMF evenly, and under the conditions of a rotation speed of 60 r / min and ultraviolet light irradiation at 365 nm, carry out the reaction for 1.5 h to obtain the starting monomer;

[0047] Step B2: Mix octamethylcyclotetrasiloxane and concentrated sulfuric acid evenly. Under the conditions of a rotation speed of 120 r / min and a temperature of 80 °C, carry out the reaction for 4 h to obtain a chain extender monomer. Mix the starting monomer, the chain extender monomer, and DMF, and under the conditions of a rotation speed of 150 r / min and a temperature of 65 °C, carry out the reaction for 10 h, then cool down to 15 °C, add dimethylchlorosilane, and continue the reaction for 10 h to obtain a modified monomer;

[0048] Step B3: Mix the modified monomer, 4-vinylphenol, chloroplatinic acid, and DMF evenly. Under the conditions of a rotation speed of 200 r / min and a temperature of 75 °C, carry out the reaction for 3 h to obtain a functional monomer. Mix the functional monomer, 2,6-dimethylphenol, copper chloride, pyridine, and DMF evenly, and under the conditions of a rotation speed of 120 r / min, a temperature of 30 °C, and an oxygen atmosphere, carry out the reaction for 2 h to obtain a functionalized polyphenylene ether.

[0049] The dosage ratios of sodium hydroxide, isopropanol, methanol, and 1,3-divinyltetramethyldisiloxane described in Step B1 are 200 mmol: 35 mL: 35 mL: 100 mmol, the molar ratio of the intermediate to pentaerythritol tetrakis(mercaptoacetate) is 4:1, and the dosage of benzophenone is 1% of the mass of the intermediate.

[0050] The dosage of concentrated sulfuric acid described in Step B2 is 1.5% of the mass of octamethylcyclotetrasiloxane, and the molar ratio of the starting monomer, the chain extender monomer, and dimethylchlorosilane is 1:4:4.2.

[0051] The molar ratio of the modified monomer to 4-vinylphenol described in Step B3 is 1:4, and the dosage ratios of the functional monomer, 2,6-dimethylphenol, copper chloride, pyridine, and DMF are 1 g: 20 g: 0.6 g: 50 mL: 200 mL.

[0052] Example 3. A preparation method of an antistatic MPPE composite based on CNT specifically includes the following steps:

[0053] Step A1: Mix functionalized polyphenylene ether, furan carbonyl chloride, 4-dimethylaminopyridine, triethylamine, and ethylene glycol dimethyl ether, and react for 1.5 h under the conditions of a rotation speed of 300 r / min and a temperature of 0 °C to obtain modified polyphenylene ether. Mix styrene, 4,4'-azobis(4-cyanopentanol), and toluene evenly, introduce nitrogen protection, and react for 12 h under the conditions of a rotation speed of 150 r / min and a temperature of 75 °C to obtain hydroxylated polystyrene;

[0054] Step A2: Mix hydroxylated polystyrene, furan carbonyl chloride, 4-dimethylaminopyridine, triethylamine, and DMF, and react for 3 h under the conditions of a rotation speed of 300 r / min and a temperature of 0 °C to obtain modified polystyrene. Disperse carbon nanotubes in ethanol, stir and add KH550 and deionized water under the conditions of a rotation speed of 300 r / min and a temperature of 70 °C, and react for 3 h to obtain amino-functionalized carbon nanotubes;

[0055] Step A3: Mix amino-functionalized carbon nanotubes, maleic anhydride, triethylamine, and toluene evenly, and reflux and react for 3 h under the conditions of a rotation speed of 80 r / min and a temperature of 120 °C to obtain modified carbon nanotubes. Weigh the following raw materials in parts by weight: 50 parts of modified polyphenylene ether, 50 parts of modified polystyrene, 15 parts of modified carbon nanotubes, and 1.5 parts of zinc oxide. Extrude and pelletize the raw materials under the condition of a temperature of 240 °C to obtain a CNT-based antistatic MPPE composite material.

[0056] The dosage ratio of the functionalized polyphenylene ether, furan carbonyl chloride, 4-dimethylaminopyridine, triethylamine, and ethylene glycol dimethyl ether described in Step A1 is 1 g: 2 g: 0.7 g: 1 mL: 50 mL, and the mass ratio of styrene, 4,4'-azobis(4-cyanopentanol), and toluene is 20: 1.2: 20.

[0057] The dosage ratio of the hydroxylated polystyrene, furan carbonyl chloride, 4-dimethylaminopyridine, triethylamine, and DMF described in Step A2 is 1 g: 1.8 g: 0.7 g: 1 mL: 50 mL, and the dosage of KH550 is 2% of the mass of the carbon nanotubes.

[0058] The dosage ratio of the amino-functionalized carbon nanotubes, maleic anhydride, triethylamine, and toluene described in Step A3 is 1 g: 50 mmol: 150 mmol: 30 mL.

[0059] The functionalized polyphenylene ether is prepared by the following steps:

[0060] Step B1: Mix sodium hydroxide, isopropanol, and methanol evenly. Under the conditions of a rotation speed of 150 r / min and a temperature of 60 °C, stir for 5 h, then add 1,3-divinyltetramethyldisiloxane and toluene, and continue the reaction for 40 min to obtain an intermediate. Mix the intermediate, pentaerythritol tetrakis(mercaptoacetate), benzophenone, and DMF evenly, and under the conditions of a rotation speed of 80 r / min and irradiation with 365 nm ultraviolet light, carry out the reaction for 1.5 h to obtain the starting monomer;

[0061] Step B2: Mix octamethylcyclotetrasiloxane and concentrated sulfuric acid evenly. Under the conditions of a rotation speed of 150 r / min and a temperature of 80 °C, carry out the reaction for 5 h to obtain a chain extender monomer. Mix the starting monomer, the chain extender monomer, and DMF, and under the conditions of a rotation speed of 200 r / min and a temperature of 65 °C, carry out the reaction for 15 h, then cool down to 15 °C, add dimethylchlorosilane, and continue the reaction for 15 h to obtain a modified monomer;

[0062] Step B3: Mix the modified monomer, 4-vinylphenol, chloroplatinic acid, and DMF evenly. Under the conditions of a rotation speed of 300 r / min and a temperature of 80 °C, carry out the reaction for 3 h to obtain a functional monomer. Mix the functional monomer, 2,6-dimethylphenol, copper chloride, pyridine, and DMF evenly, and under the conditions of a rotation speed of 150 r / min, a temperature of 30 °C, and an oxygen atmosphere, carry out the reaction for 3 h to obtain a functionalized polyphenylene ether.

[0063] The dosage ratio of sodium hydroxide, isopropanol, methanol, and 1,3-divinyltetramethyldisiloxane described in Step B1 is 200 mmol: 35 mL: 35 mL: 100 mmol, the molar ratio of the intermediate to pentaerythritol tetrakis(mercaptoacetate) is 4:1, and the dosage of benzophenone is 1% of the mass of the intermediate.

[0064] The dosage of concentrated sulfuric acid described in Step B2 is 1.5% of the mass of octamethylcyclotetrasiloxane, and the molar ratio of the starting monomer, the chain extender monomer, and dimethylchlorosilane is 1:4:4.2.

[0065] The molar ratio of the modified monomer to 4-vinylphenol described in Step B3 is 1:4, and the dosage ratio of the functional monomer, 2,6-dimethylphenol, copper chloride, pyridine, and DMF is 1 g: 20 g: 0.6 g: 50 mL: 200 mL.

[0066] Comparative Example 1: In this comparative example, compared with Example 1, carbon nanotubes are used instead of modified carbon nanotubes, and the remaining steps are the same.

[0067] Comparative Example 2: In this comparative example, compared with Example 1, functionalized polyphenylene ether is used instead of modified polyphenylene ether, and the remaining steps are the same.

[0068] Comparative Example 3: Compared with Example 1, ethylene glycol dithiol was used instead of pentaerythritol tetrakis(mercaptoacetate), and the remaining steps were the same.

[0069] Comparative Example 4: Compared with Example 1, bisphenol A was used instead of the functional monomer, and the remaining steps were the same.

[0070] The composite materials prepared in Examples 1-3 and Comparative Examples 1-4 were made into Type 1A specimens according to the standard of GB / T 1040.1-2018 to detect the tensile strength, and made into Type A specimens according to the standard of GB / T 1843-2008 to detect the impact strength. The test results are shown in Table 1 below.

[0071] Table 1

[0072]

[0073] It can be seen from Table 1 that this application has good mechanical properties.

[0074] The above content is only an example and illustration of the concept of the present invention. Those skilled in the art of this technology can make various modifications or supplements to the specific embodiments described, or use similar methods to replace them. As long as they do not deviate from the concept of the invention or exceed the scope defined by this claim book, they should all belong to the protection scope of the present invention.

Claims

1. A method for preparing an antistatic MPPE composite material based on CNT, characterized in that: The specific steps include: Step A1: functionalized polyphenylene ether, furanoyl chloride, 4-dimethylaminopyridine, triethylamine and ethylene glycol dimethyl ether are mixed and reacted to obtain modified polyphenylene ether, styrene, 4,4'-azobis(4-cyanopentanol) and toluene are uniformly mixed, nitrogen is introduced for protection, and the mixture is reacted to obtain hydroxylated polystyrene; Step A2: hydroxylated polystyrene, furanoyl chloride, 4-dimethylaminopyridine, triethylamine and DMF are mixed and reacted to obtain modified polystyrene, carbon nanotubes are dispersed in ethanol, stirred and KH550 and deionized water are added to react to obtain amino carbon nanotubes; Step A3: mixing the aminated carbon nanotubes, maleic anhydride, triethylamine and toluene for reflux reaction to obtain modified carbon nanotubes, weighing the following raw materials in parts by weight: 40-50 parts of modified polyphenylene ether, 40-50 parts of modified polystyrene, 10-15 parts of modified carbon nanotubes and 1-1.5 parts of zinc oxide, extruding and granulating the raw materials to obtain an antistatic MPPE composite material based on CNT; The functionalized polyphenylene ether is prepared by the following steps: Step B1: After mixing and stirring sodium hydroxide, isopropanol and methanol, 1,3-divinyltetramethyldisiloxane and toluene are added to react to obtain an intermediate, and the intermediate, pentaerythritol tetrathioglycolate, benzophenone and DMF are mixed to react to obtain a starting monomer; Step B2: octamethylcyclotetrasiloxane and concentrated sulfuric acid are mixed and reacted to obtain a chain extension monomer, and the starting monomer, the chain extension monomer and DMF are mixed and reacted, and then the temperature is reduced and dimethylchlorosilane is added to continue the reaction to obtain a modified monomer; Step B3: The modified monomer, 4-vinylphenol, chloroplatinic acid and DMF are mixed and reacted to obtain a functional monomer, and the functional monomer, 2,6-dimethylphenol, cupric chloride, pyridine and DMF are mixed and reacted to obtain a functionalized polyphenylene ether.

2. The method for preparing an antistatic MPPE composite material based on CNT according to claim 1, characterized in that: The amount ratio of the functionalized polyphenylene ether, furanyl chloride, 4-dimethylaminopyridine, triethylamine and ethylene glycol dimethyl ether described in step A1 is 1 g:2 g:0.7 g:1 mL:50 mL, and the mass ratio of styrene, 4,4'-azobis(4-cyanopentanol) and toluene is 20:1.2:

20.

3. The method for preparing an antistatic MPPE composite material based on CNT according to claim 1, characterized in that: The amount ratio of hydroxylated polystyrene, furanoyl chloride, 4-dimethylaminopyridine, triethylamine and DMF described in step A2 is 1 g:1.8 g:0.7 g:1 mL:50 mL, and the amount of KH550 is 2% of the mass of the carbon nanotubes.

4. The method for preparing an antistatic MPPE composite material based on CNT according to claim 1, characterized in that: The amount ratio of the amino carbon nanotubes, maleic anhydride, triethylamine and toluene described in step A3 is 1 g:50 mmol:150 mmol:30 mL.

5. The method for preparing an antistatic MPPE composite material based on CNT according to claim 1, characterized in that: The amount ratio of sodium hydroxide, isopropanol, methanol and 1,3-divinyltetramethyldisiloxane in step B1 is 200mmol:35mL:35mL:100mmol, and the molar ratio of the intermediate to pentaerythritol tetrathioglycolate is 4:

1.

6. The method for preparing an antistatic MPPE composite material based on CNT according to claim 1, characterized in that: The amount of concentrated sulfuric acid used in step B2 is 1.5% of the mass of octamethylcyclotetrasiloxane, and the molar ratio of the starting monomer, the chain extension monomer and dimethylchlorosilane is 1:4:4.

2.

7. The method for preparing an antistatic MPPE composite material based on CNT according to claim 1, characterized in that: The molar ratio of the modified monomer and 4-vinylphenol described in step B3 is 1:4, and the amount ratio of the functional monomer, 2,6-dimethylphenol, copper chloride, pyridine and DMF is 1g:20g:0.6g:50mL:200mL.

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

Images