Antistatic PPO material and preparation method thereof

Abstract

The invention discloses an antistatic PPO material and a preparation method thereof.The preparation method comprises the steps that aminated polyphenyl ether and a modifier react, amino on the aminated polyphenyl ether and epoxy on the modifier react, modified polyphenyl ether is prepared, the modified polyphenyl ether and lauroyl chloride react, and the antistatic PPO material is prepared. A molecular side chain of the antistatic PPO material contains a large number of quaternary ammonium salt structures, quaternary ammonium salt cations in the material are subjected to jumping type migration through pores between adjacent molecules to form an ion conductive path, and anions or water molecules in the environment are adsorbed on the surface of the material through static electricity to form an ion transmission network, so that the antistatic PPO material is prepared. According to the present invention, the side chain contains the long-chain alkyl group, the long-chain alkyl group can increase the distance between the molecular chains so as to easily move the chain segments of the main chain and the side chain of the polymer, and the addition of the borate and the imine structure further improves the toughness of the material so as to improve the mechanical property of the material.

Description

Technical Field

[0001] This invention relates to the field of PPO material preparation technology, specifically to an antistatic PPO material and its preparation method. Background Technology

[0002] In recent years, with the widespread use of electronic products, the demand for antistatic materials has been increasing. Especially in the production of electronic components, electrostatic discharge can cause irreversible damage to equipment, directly affecting product reliability and production efficiency. Antistatic PPO materials, due to their excellent mechanical properties and chemical stability, have become one of the most widely used materials in the electronics industry. As a polymer, PPO has excellent high-temperature resistance, mechanical strength, and dimensional stability. However, traditional PPO materials are prone to static electricity due to their high surface resistivity, especially in dry environments. This often leads to the static attraction of dust or light particles, affecting the cleanliness and aesthetics of the product surface. Furthermore, PPO materials have poor impact resistance and can break under external forces during processing. Summary of the Invention

[0003] The purpose of this invention is to provide an antistatic PPO material and its preparation method, which solves the problems of poor antistatic effect and easy damage when subjected to impact of current PPO materials.

[0004] The objective of this invention can be achieved through the following technical solutions: A method for preparing an antistatic PPO material specifically includes the following steps: Step A1: Mix 3,5-dihydroxybenzyl alcohol, potassium carbonate, and acetone, purge with nitrogen, and stir for 20-30 minutes at a speed of 150-200 r / min and a temperature of 25-30℃. Then add 18-crown ether-6 and 3-(dimethylamino)chloropropane hydrochloride, heat to 58-60℃, and react for 30-35 hours to obtain intermediate 1. Mix intermediate 1, potassium iodide, and methanol evenly, and react for 30-35 hours at a speed of 30-35℃ to obtain intermediate 2. Step A2: Mix intermediate 2, boron trifluoride ethyl ether, epichlorohydrin and DMF evenly, and react for 2-3 hours at a speed of 200-300 r / min and a temperature of 65-70℃. Then add sodium hydroxide solution, raise the temperature to 75-80℃, and continue the reaction for 3-5 hours to obtain the modifier. Mix 2,6-dimethylphenol, 3,5-dimethyl-4-hydroxybenzaldehyde and toluene evenly, and stir at a speed of 200-300 r / min and a temperature of 30-35℃. Add cuprous bromide and tetramethylethylenediamine, introduce oxygen, and react for 3-5 hours to obtain pretreated polyphenylene ether. Step A3: Dissolve the pretreated polyphenylene ether in carbon tetrachloride, purge with nitrogen, and stir at 120-150 r / min and 60-65℃, adding N-bromosuccinimide and azobisisobutyronitrile, and react for 15-20 h to obtain brominated polyphenylene ether. Mix the brominated polyphenylene ether, modifying additive, 4A molecular sieve, p-toluenesulfonic acid and dimethylacetamide evenly, and reflux at 150-200 r / min and 165-168℃ for 8-10 h to obtain functionalized polyphenylene ether. Dissolve the functionalized polyphenylene ether in dimethylacetamide, purge with nitrogen, and stir at 600-800 r / min and 0℃, adding concentrated ammonia, and heat to 20-25℃ for 2-4 h. Adjust the pH to 12 to obtain aminated polyphenylene ether. Step A4: Dissolve the aminated polyphenylene ether in DMF, purge with nitrogen, and stir while adding the modifier at a speed of 150-200 r / min, a temperature of 40-50℃, and a pH of 11-12 for 8-10 hours to obtain the modified polyphenylene ether. Mix the modified polyphenylene ether, triethylamine, 4-dimethylaminopyridine, and ethylene glycol dimethyl ether evenly, purge with nitrogen, and stir while adding lauroyl chloride at a speed of 200-300 r / min and a temperature of 0℃ for 3-5 hours to obtain the antistatic PPO material.

[0005] Furthermore, the molar ratio of 3,5-dihydroxybenzyl alcohol, potassium carbonate, 18-crown ether-6 and 3-(dimethylamino)chloropropane hydrochloride in step A1 is 15:45:7.5:30, and the molar ratio of intermediate 1 and potassium iodide is 1:4.

[0006] Furthermore, in step A2, the ratio of intermediate 2, boron trifluoride ether, epichlorohydrin, and sodium hydroxide solution is 30 mmol:0.9 g:30 mmol:4 mL, the mass fraction of sodium hydroxide solution is 25%, the ratio of 2,6-dimethylphenol, 3,5-dimethyl-4-hydroxybenzaldehyde, cuprous bromide, and tetramethylethylenediamine is 5 g:25 g:0.45 g:0.6 mL, and the oxygen introduction rate is 1 L / min.

[0007] Furthermore, in step A3, the molar ratio of pretreated polyphenylene ether, N-bromosuccinimide, and azobisisobutyronitrile is 25:10:1; the dosage ratio of brominated polyphenylene ether, modified additive, and 4A molecular sieve is 20 mmol:5 mmol:4 g; the dosage of p-toluenesulfonic acid is 1‰ of the mass of the modified additive; the dosage ratio of bromine atoms on the functionalized polyphenylene ether to concentrated ammonia is 1 mol:1.5 L; and the mass fraction of concentrated ammonia is 28%.

[0008] Furthermore, in step A4, the molar ratio of amino groups on the aminated polyphenylene ether to the modifier is 1:1, and the molar ratio of hydroxyl groups, triethylamine, 4-dimethylaminopyridine, and lauroyl chloride on the modified polyphenylene ether is 1:1.2:0.8:1.

[0009] Furthermore, the modified additive is prepared by the following steps: Step B1: Mix lithium dimethylvinylsilane and tetrahydrofuran evenly, stir and add hexamethylcyclotrisiloxane at a speed of 200-300 r / min and a temperature of 0℃, raise the temperature to 20-25℃ and react for 8-10 h, then add tetrachlorosilane and react for 1-1.5 h to obtain polysiloxane. Step B2: Mix polysiloxane, thioglycerol, benzoin dimethyl ether and p-xylene evenly, purge with nitrogen, and react for 30-40 minutes under the conditions of 150-200 r / min and 365 nm ultraviolet light irradiation to obtain pretreated polysiloxane. Step B3: Mix the pretreated polysiloxane, p-aminophenylboronic acid, 4A molecular sieve and p-xylene evenly, purge with nitrogen, and react for 4-6 hours at a rotation speed of 200-300 r / min, a temperature of 138-142℃ and a pH of 5-6. Adjust the pH to 7.5-8 to obtain the modified additive.

[0010] Furthermore, the molar ratio of Si-Cl bonds on lithium dimethylvinylsilanolate, hexamethylcyclotrisiloxane, and tetrachlorosilane in step B1 is 1:4:1.

[0011] Furthermore, the molar ratio of polysiloxane and thioglycerol in step B2 is 1:4, and the amount of benzoin dimethyl ether used is 1% of the mass of thioglycerol.

[0012] Furthermore, the ratio of polysiloxane, p-aminophenylboronic acid, and 4A molecular sieve used in step B3 is 10 mmol: 40 mmol: 7 g.

[0013] The beneficial effects of this invention: The antistatic PPO material disclosed in this invention uses 3,5-dihydroxybenzyl alcohol as a raw material and reacts it with 3-(dimethylamino)chloropropane hydrochloride, causing the phenolic hydroxyl groups on 3,5-dihydroxybenzyl alcohol to react with the chlorine atom sites on 3-(dimethylamino)chloropropane hydrochloride, to obtain intermediate 1. Intermediate 1 is reacted with potassium iodide to form a quaternary ammonium salt structure, to obtain intermediate 2. Intermediate 2 is reacted with epichlorohydrin, causing the alcoholic hydroxyl groups on intermediate 2 to react with the epoxy groups on epichlorohydrin, and then the ring is closed under the action of sodium hydroxide solution to form a new epoxy group, to obtain a modifier. 2,6-Dimethylphenol and 3,5-dimethyl- 4-Hydroxybenzaldehyde reacts to form polyphenylene ether segments containing terminal aldehyde groups, yielding pretreated polyphenylene ether. The pretreated polyphenylene ether is treated with N-bromosuccinimide to branch bromine onto the side chains, yielding brominated polyphenylene ether. The brominated polyphenylene ether is reacted with a modifying additive, causing the aldehyde groups on the brominated polyphenylene ether to react with the amino groups on the modifying additive, yielding functionalized polyphenylene ether. The functionalized polyphenylene ether is treated with concentrated ammonia to form amino groups on the side chains, yielding aminated polyphenylene ether. The aminated polyphenylene ether is reacted with a modifier, causing the amino groups on the aminated polyphenylene ether to react with the epoxy groups on the modifier, yielding modified polyphenylene ether. The modified polyphenylene ether is reacted with lauroyl chloride to obtain an antistatic PPO material.

[0014] The modified additive uses lithium dimethylvinylsilanolate as an initiator and hexamethylcyclotrisiloxane as a polymerization monomer, and then adds tetrachlorosilane to react the Si-Cl bonds on lithium silanolate and tetrachlorosilane to obtain polysiloxane. The polysiloxane is then reacted with thioglycerol to react the double bonds on the polysiloxane with the mercapto groups on the thioglycerol to obtain pretreated polysiloxane. The pretreated polysiloxane is then reacted with p-aminophenylboronic acid to react the diol on the pretreated polysiloxane with the boric acid on the p-aminophenylboronic acid to form a borate ester structure, thus obtaining the modified additive.

[0015] This antistatic PPO material contains a large number of quaternary ammonium salt structures in its molecular side chains. Inside the material, quaternary ammonium salt cations migrate in a hopping manner through the pores between adjacent molecules, forming ion-conducting pathways. On the material surface, they electrostatically adsorb anions or water molecules in the environment, forming an ion transport network, which gives the material a good antistatic effect. The individual molecular segments have a cross structure, and the side chains contain long-chain alkyl groups. Long-chain alkyl groups can increase the spacing between molecular chains, making it easier for the polymer main chain and side chain segments to move. Furthermore, the addition of borate esters and imine structures further improves the toughness of the material, thereby increasing its mechanical properties. Detailed Implementation

[0016] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0017] Example 1: A method for preparing an antistatic PPO material, specifically including the following steps: Step A1: Mix 3,5-dihydroxybenzyl alcohol, potassium carbonate, and acetone, and purge with nitrogen. Stir for 20 min at 150 r / min and 25 °C. Then add 18-crown ether-6 and 3-(dimethylamino)chloropropane hydrochloride, heat to 58 °C, and react for 30 h to obtain intermediate 1. Mix intermediate 1, potassium iodide, and methanol evenly and react for 30 h at 30 °C to obtain intermediate 2. Step A2: Mix intermediate 2, boron trifluoride ethyl ether, epichlorohydrin and DMF evenly, and react for 2 hours at 200 r / min and 65°C. Then add sodium hydroxide solution, raise the temperature to 75°C and continue the reaction for 3 hours to obtain the modifier. Mix 2,6-dimethylphenol, 3,5-dimethyl-4-hydroxybenzaldehyde and toluene evenly, and stir at 200 r / min and 30°C. Add cuprous bromide and tetramethylethylenediamine, introduce oxygen and react for 3 hours to obtain pretreated polyphenylene ether. Step A3: Dissolve the pretreated polyphenylene ether in carbon tetrachloride, purge with nitrogen, and stir at 120 r / min and 60°C. Add N-bromosuccinimide and azobisisobutyronitrile and react for 15 h to obtain brominated polyphenylene ether. Mix brominated polyphenylene ether, modified additive, 4A molecular sieve, p-toluenesulfonic acid and dimethylacetamide evenly, and reflux at 150 r / min and 165°C for 8 h to obtain functionalized polyphenylene ether. Dissolve the functionalized polyphenylene ether in dimethylacetamide, purge with nitrogen, and stir at 600 r / min and 0°C. Add concentrated ammonia, heat to 20°C, and react for 2 h. Adjust the pH to 12 to obtain aminated polyphenylene ether. Step A4: Dissolve the aminated polyphenylene ether in DMF, purge with nitrogen, and stir with a modifier at a speed of 150 r / min, a temperature of 40℃, and a pH of 11 for 8 hours to obtain modified polyphenylene ether. Mix the modified polyphenylene ether, triethylamine, 4-dimethylaminopyridine, and ethylene glycol dimethyl ether evenly, purge with nitrogen, stir with lauroyl chloride at a speed of 200 r / min and a temperature of 0℃ for 3 hours to obtain antistatic PPO material.

[0018] The molar ratio of 3,5-dihydroxybenzyl alcohol, potassium carbonate, 18-crown ether-6 and 3-(dimethylamino)chloropropane hydrochloride in step A1 is 15:45:7.5:30, and the molar ratio of intermediate 1 and potassium iodide is 1:4.

[0019] In step A2, the ratio of intermediate 2, boron trifluoride ether, epichlorohydrin, and sodium hydroxide solution is 30 mmol: 0.9 g: 30 mmol: 4 mL, the mass fraction of sodium hydroxide solution is 25%, the ratio of 2,6-dimethylphenol, 3,5-dimethyl-4-hydroxybenzaldehyde, cuprous bromide, and tetramethylethylenediamine is 5 g: 25 g: 0.45 g: 0.6 mL, and the oxygen introduction rate is 1 L / min.

[0020] The molar ratio of pretreated polyphenylene ether, N-bromosuccinimide and azobisisobutyronitrile in step A3 is 25:10:1; the ratio of brominated polyphenylene ether, modified additive and 4A molecular sieve is 20mmol:5mmol:4g; the amount of p-toluenesulfonic acid is 1‰ of the mass of the modified additive; the ratio of bromine atoms on the functionalized polyphenylene ether to concentrated ammonia is 1mol:1.5L; and the mass fraction of concentrated ammonia is 28%.

[0021] The molar ratio of amino groups and modifiers on the aminated polyphenylene ether described in step A4 is 1:1, and the molar ratio of hydroxyl groups, triethylamine, 4-dimethylaminopyridine, and lauroyl chloride on the modified polyphenylene ether is 1:1.2:0.8:1.

[0022] The modified additive is prepared by the following steps: Step B1: Dimethylvinylsilane lithium and tetrahydrofuran are mixed evenly, stirred and hexamethylcyclotrisiloxane is added at a speed of 200 r / min and a temperature of 0℃, the temperature is raised to 20℃ and reacted for 8 h, then tetrachlorosilane is added and reacted for 1 h to obtain polysiloxane. Step B2: Mix polysiloxane, thioglycerol, benzoin dimethyl ether and p-xylene evenly, purge with nitrogen, and react for 30 min under the conditions of 150 r / min and 365 nm ultraviolet light irradiation to obtain pretreated polysiloxane. Step B3: Mix the pretreated polysiloxane, p-aminophenylboronic acid, 4A molecular sieve and p-xylene evenly, purge with nitrogen, and react for 4 hours at a speed of 200 r / min, a temperature of 138℃ and a pH of 5. Adjust the pH to 7.5 to obtain the modified additive.

[0023] The molar ratio of Si-Cl bonds on lithium dimethylvinylsilanolate, hexamethylcyclotrisiloxane, and tetrachlorosilane in step B1 is 1:4:1.

[0024] The molar ratio of polysiloxane and thioglycerol in step B2 is 1:4, and the amount of benzoin dimethyl ether used is 1% of the mass of thioglycerol.

[0025] The ratio of polysiloxane, p-aminophenylboronic acid and 4A molecular sieve used in step B3 is 10 mmol: 40 mmol: 7 g.

[0026] Example 2, a method for preparing an antistatic PPO material, specifically includes the following steps: Step A1: Mix 3,5-dihydroxybenzyl alcohol, potassium carbonate, and acetone, and purge with nitrogen. Stir at 150 r / min and 30°C for 25 min. Then add 18-crown ether-6 and 3-(dimethylamino)chloropropane hydrochloride, and heat to 58°C for 35 h to obtain intermediate 1. Mix intermediate 1, potassium iodide, and methanol evenly and react at 30°C for 35 h to obtain intermediate 2. Step A2: Intermediate 2, boron trifluoride ethyl ether, epichlorohydrin and DMF are mixed evenly and reacted at 200 r / min and 70°C for 2 hours. Then sodium hydroxide solution is added, the temperature is raised to 80°C, and the reaction continues for 4 hours to obtain the modifier. 2,6-dimethylphenol, 3,5-dimethyl-4-hydroxybenzaldehyde and toluene are mixed evenly and stirred at 200 r / min and 35°C. Cuprous bromide and tetramethylethylenediamine are added, oxygen is introduced, and the reaction is carried out for 4 hours to obtain the pretreated polyphenylene ether. Step A3: Dissolve the pretreated polyphenylene ether in carbon tetrachloride, purge with nitrogen, and stir at 120 r / min and 65°C. Add N-bromosuccinimide and azobisisobutyronitrile and react for 18 h to obtain brominated polyphenylene ether. Mix brominated polyphenylene ether, modifying additive, 4A molecular sieve, p-toluenesulfonic acid and dimethylacetamide evenly, and reflux at 150 r / min and 168°C for 9 h to obtain functionalized polyphenylene ether. Dissolve the functionalized polyphenylene ether in dimethylacetamide, purge with nitrogen, and stir at 600 r / min and 0°C. Add concentrated ammonia, raise the temperature to 25°C, and react for 3 h. Adjust the pH to 12 to obtain aminated polyphenylene ether. Step A4: Dissolve the aminated polyphenylene ether in DMF, purge with nitrogen, and stir with a modifier at a speed of 150 r / min, a temperature of 45℃, and a pH of 12 for 8-10 hours to obtain modified polyphenylene ether. Mix the modified polyphenylene ether, triethylamine, 4-dimethylaminopyridine, and ethylene glycol dimethyl ether evenly, purge with nitrogen, and stir with lauroyl chloride at a speed of 200 r / min and a temperature of 0℃ for 4 hours to obtain antistatic PPO material.

[0027] The molar ratio of 3,5-dihydroxybenzyl alcohol, potassium carbonate, 18-crown ether-6 and 3-(dimethylamino)chloropropane hydrochloride in step A1 is 15:45:7.5:30, and the molar ratio of intermediate 1 and potassium iodide is 1:4.

[0028] In step A2, the ratio of intermediate 2, boron trifluoride ether, epichlorohydrin, and sodium hydroxide solution is 30 mmol: 0.9 g: 30 mmol: 4 mL, the mass fraction of sodium hydroxide solution is 25%, the ratio of 2,6-dimethylphenol, 3,5-dimethyl-4-hydroxybenzaldehyde, cuprous bromide, and tetramethylethylenediamine is 5 g: 25 g: 0.45 g: 0.6 mL, and the oxygen introduction rate is 1 L / min.

[0029] The molar ratio of pretreated polyphenylene ether, N-bromosuccinimide and azobisisobutyronitrile in step A3 is 25:10:1; the ratio of brominated polyphenylene ether, modified additive and 4A molecular sieve is 20mmol:5mmol:4g; the amount of p-toluenesulfonic acid is 1‰ of the mass of the modified additive; the ratio of bromine atoms on the functionalized polyphenylene ether to concentrated ammonia is 1mol:1.5L; and the mass fraction of concentrated ammonia is 28%.

[0030] The molar ratio of amino groups and modifiers on the aminated polyphenylene ether described in step A4 is 1:1, and the molar ratio of hydroxyl groups, triethylamine, 4-dimethylaminopyridine, and lauroyl chloride on the modified polyphenylene ether is 1:1.2:0.8:1.

[0031] The modified additive is prepared by the following steps: Step B1: Dimethylvinylsilane lithium and tetrahydrofuran are mixed evenly, stirred and hexamethylcyclotrisiloxane is added at a speed of 300 r / min and a temperature of 0℃, the temperature is raised to 20℃ and reacted for 9 h, then tetrachlorosilane is added and reacted for 1.3 h to obtain polysiloxane. Step B2: Mix polysiloxane, thioglycerol, benzoin dimethyl ether and p-xylene evenly, purge with nitrogen, and react for 35 min under the conditions of 150 r / min and 365 nm ultraviolet light irradiation to obtain pretreated polysiloxane. Step B3: Mix the pretreated polysiloxane, p-aminophenylboronic acid, 4A molecular sieve and p-xylene evenly, purge with nitrogen, and react for 5 hours at a speed of 200 r / min, a temperature of 140℃ and a pH of 6. Adjust the pH to 7.5 to obtain the modified additive.

[0032] The molar ratio of Si-Cl bonds on lithium dimethylvinylsilanolate, hexamethylcyclotrisiloxane, and tetrachlorosilane in step B1 is 1:4:1.

[0033] The molar ratio of polysiloxane and thioglycerol in step B2 is 1:4, and the amount of benzoin dimethyl ether used is 1% of the mass of thioglycerol.

[0034] The ratio of polysiloxane, p-aminophenylboronic acid and 4A molecular sieve used in step B3 is 10 mmol: 40 mmol: 7 g.

[0035] Example 3, a method for preparing an antistatic PPO material, specifically includes the following steps: Step A1: Mix 3,5-dihydroxybenzyl alcohol, potassium carbonate, and acetone, and purge with nitrogen. Stir at 200 r / min and 30°C for 30 min. Then add 18-crown ether-6 and 3-(dimethylamino)chloropropane hydrochloride, heat to 60°C, and react for 35 h to obtain intermediate 1. Mix intermediate 1, potassium iodide, and methanol evenly and react at 35°C for 35 h to obtain intermediate 2. Step A2: Mix intermediate 2, boron trifluoride ethyl ether, epichlorohydrin and DMF evenly, and react for 3 hours at 300 r / min and 70°C. Then add sodium hydroxide solution, raise the temperature to 80°C and continue the reaction for 5 hours to obtain the modifier. Mix 2,6-dimethylphenol, 3,5-dimethyl-4-hydroxybenzaldehyde and toluene evenly, and stir at 300 r / min and 35°C. Add cuprous bromide and tetramethylethylenediamine, introduce oxygen and react for 5 hours to obtain pretreated polyphenylene ether. Step A3: Dissolve the pretreated polyphenylene ether in carbon tetrachloride, purge with nitrogen, and stir at 150 r / min and 65°C. Add N-bromosuccinimide and azobisisobutyronitrile and react for 20 h to obtain brominated polyphenylene ether. Mix the brominated polyphenylene ether, modified additive, 4A molecular sieve, p-toluenesulfonic acid and dimethylacetamide evenly, and reflux at 200 r / min and 168°C for 10 h to obtain functionalized polyphenylene ether. Dissolve the functionalized polyphenylene ether in dimethylacetamide, purge with nitrogen, and stir at 800 r / min and 0°C. Add concentrated ammonia, raise the temperature to 25°C, and react for 4 h. Adjust the pH to 12 to obtain aminated polyphenylene ether. Step A4: Dissolve the aminated polyphenylene ether in DMF, purge with nitrogen, and stir with a modifier at a speed of 200 r / min, a temperature of 50℃, and a pH of 12 for 10 h to obtain the modified polyphenylene ether. Mix the modified polyphenylene ether, triethylamine, 4-dimethylaminopyridine, and ethylene glycol dimethyl ether evenly, purge with nitrogen, stir with lauroyl chloride at a speed of 300 r / min and a temperature of 0℃ for 5 h to obtain the antistatic PPO material.

[0036] The molar ratio of 3,5-dihydroxybenzyl alcohol, potassium carbonate, 18-crown ether-6 and 3-(dimethylamino)chloropropane hydrochloride in step A1 is 15:45:7.5:30, and the molar ratio of intermediate 1 and potassium iodide is 1:4.

[0037] In step A2, the ratio of intermediate 2, boron trifluoride ether, epichlorohydrin, and sodium hydroxide solution is 30 mmol: 0.9 g: 30 mmol: 4 mL, the mass fraction of sodium hydroxide solution is 25%, the ratio of 2,6-dimethylphenol, 3,5-dimethyl-4-hydroxybenzaldehyde, cuprous bromide, and tetramethylethylenediamine is 5 g: 25 g: 0.45 g: 0.6 mL, and the oxygen introduction rate is 1 L / min.

[0038] The molar ratio of pretreated polyphenylene ether, N-bromosuccinimide and azobisisobutyronitrile in step A3 is 25:10:1; the ratio of brominated polyphenylene ether, modified additive and 4A molecular sieve is 20mmol:5mmol:4g; the amount of p-toluenesulfonic acid is 1‰ of the mass of the modified additive; the ratio of bromine atoms on the functionalized polyphenylene ether to concentrated ammonia is 1mol:1.5L; and the mass fraction of concentrated ammonia is 28%.

[0039] The molar ratio of amino groups and modifiers on the aminated polyphenylene ether described in step A4 is 1:1, and the molar ratio of hydroxyl groups, triethylamine, 4-dimethylaminopyridine, and lauroyl chloride on the modified polyphenylene ether is 1:1.2:0.8:1.

[0040] The modified additive is prepared by the following steps: Step B1: Dimethylvinylsilane lithium and tetrahydrofuran are mixed evenly, stirred and hexamethylcyclotrisiloxane is added at a speed of 300 r / min and a temperature of 0℃, the temperature is raised to 25℃ and reacted for 10 h, then tetrachlorosilane is added and reacted for 1.5 h to obtain polysiloxane. Step B2: Mix polysiloxane, thioglycerol, benzoin dimethyl ether and p-xylene evenly, purge with nitrogen, and react for 40 min under the conditions of 200 r / min and 365 nm ultraviolet light irradiation to obtain pretreated polysiloxane. Step B3: Mix the pretreated polysiloxane, p-aminophenylboronic acid, 4A molecular sieve and p-xylene evenly, purge with nitrogen, and react for 6 hours at a rotation speed of 300 r / min, a temperature of 142℃ and a pH of 6. Adjust the pH to 8 to obtain the modified additive.

[0041] The molar ratio of Si-Cl bonds on lithium dimethylvinylsilanolate, hexamethylcyclotrisiloxane, and tetrachlorosilane in step B1 is 1:4:1.

[0042] The molar ratio of polysiloxane and thioglycerol in step B2 is 1:4, and the amount of benzoin dimethyl ether used is 1% of the mass of thioglycerol.

[0043] The ratio of polysiloxane, p-aminophenylboronic acid and 4A molecular sieve used in step B3 is 10 mmol: 40 mmol: 7 g.

[0044] Comparative Example 1: In this comparative example, p-hydroxybenzyl alcohol is used instead of 3,5-dihydroxybenzyl alcohol, while the other steps are the same as in Example 1.

[0045] Comparative Example 2: In this comparative example, diphenyl dichlorosilane was used instead of tetrachlorosilane, while the other steps were the same as in Example 1.

[0046] Comparative Example 3: This comparative example uses ethylenediamine instead of the modifying additive compared to Example 1, with the remaining steps being the same.

[0047] A circular disc with a diameter of 100 mm and a thickness of 2 mm was prepared. The surface resistance was tested at a temperature of 25℃ and a humidity of 33%. According to the standard GB / T1843-2008, a type A sample was prepared and the impact strength was tested. The test results are shown in Table 1 below.

[0048] Table 1

[0049] As shown in Table 1, this application has antistatic effect and good impact resistance.

[0050] The above description is merely an example and illustration of the concept of the present invention. Those skilled in the art can make various modifications or additions 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 in the claims, they should all fall within the protection scope of the present invention.

Claims

1. A process for the preparation of an antistatic PPO material, characterized in that: Specifically comprising the following steps: Step A1: 3, 5-dihydroxybenzyl alcohol, potassium carbonate and acetone are mixed, nitrogen is introduced for protection, stirring treatment is carried out, then 18-crown-6 and 3- (dimethylamino) chloropropane hydrochloride are added, reaction is carried out, intermediate 1 is prepared, intermediate 1, potassium iodide and methanol are mixed and reacted, intermediate 2 is prepared; Step A2: intermediate 2, boron trifluoride etherate, epichlorohydrin and DMF are mixed and reacted, then sodium hydroxide solution is added, continuous reaction is carried out, a modifier is prepared, 2, 6-dimethylphenol, 3, 5-dimethyl-4-hydroxybenzaldehyde and toluene are mixed and stirred, then cuprous bromide and tetramethyl ethylenediamine are added, oxygen is introduced, reaction is carried out, and pretreated polyphenyl ether is prepared; Step A3: the pretreated polyphenyl ether is dissolved in carbon tetrachloride, nitrogen is introduced for protection, stirring is carried out, then N-bromosuccinimide and azobisisobutyronitrile are added, reaction is carried out, brominated polyphenyl ether is prepared, brominated polyphenyl ether, modified additive, 4A molecular sieve, p-toluenesulfonic acid and dimethylacetamide are mixed and refluxed, functionalized polyphenyl ether is prepared, the functionalized polyphenyl ether is dissolved in dimethylacetamide, nitrogen is introduced for protection, stirring is carried out, then concentrated ammonia is added, reaction is carried out, and aminated polyphenyl ether is prepared; Step A4: the aminated polyphenyl ether is dissolved in DMF, nitrogen is introduced for protection, stirring is carried out, then the modifier is added, reaction is carried out, modified polyphenyl ether is prepared, the modified polyphenyl ether, triethylamine, 4-dimethylamino pyridine and ethylene glycol dimethyl ether are uniformly mixed, nitrogen is introduced for protection, stirring is carried out, then lauroyl chloride is added, reaction is carried out, and antistatic PPO material is prepared.

2. The process for the preparation of an antistatic PPO material according to claim 1, characterized in that: The molar ratio of 3, 5-dihydroxybenzyl alcohol, potassium carbonate, 18-crown-6 and 3- (dimethylamino) chloropropane hydrochloride in step A1 is 15:45:7.5:30, and the molar ratio of intermediate 1 and potassium iodide is 1:

4.

3. The process for the preparation of an antistatic PPO material according to claim 1, characterized in that: The dosage ratio of intermediate 2, boron trifluoride etherate, epichlorohydrin and sodium hydroxide solution in step A2 is 30mmol:0.9g:30mmol:4mL, and the dosage ratio of 2, 6-dimethylphenol, 3, 5-dimethyl-4-hydroxybenzaldehyde, cuprous bromide and tetramethyl ethylenediamine is 5g:25g:0.45g:0.6mL.

4. The process for the preparation of an antistatic PPO material according to claim 1, characterized in that: The molar ratio of pretreated polyphenyl ether, N-bromosuccinimide and azobisisobutyronitrile in step A3 is 25:10:1, the dosage ratio of brominated polyphenyl ether, modified additive and 4A molecular sieve is 20mmol:5mmol:4g, and the dosage ratio of bromine atoms on the functionalized polyphenyl ether and concentrated ammonia is 1mol:1.5L.

5. The process for the preparation of an antistatic PPO material according to claim 1, characterized in that: The molar ratio of amino groups on the aminated polyphenyl ether and the modifier in step A4 is 1:1, and the molar ratio of hydroxyl groups on the modified polyphenyl ether, triethylamine, 4-dimethylamino pyridine and lauroyl chloride is 1:1.2:0.8:

1.

6. The process for the preparation of an antistatic PPO material according to claim 1, characterized in that: The modifier is prepared by the following steps: Step B1: dimethylvinylsilanol lithium and tetrahydrofuran are mixed and stirred, then hexamethylcyclotrisiloxane is added, reaction is carried out, then tetrachlorosilane is added, reaction is carried out, and polysiloxane is prepared; Step B2: the polysiloxane, thioglycerol, benzoin and p-xylene were mixed and irradiated by UV light to prepare a pretreated polysiloxane; Step B3: the pretreated polysiloxane, p-aminobenzoic acid, 4A molecular sieve and p-xylene were mixed and reacted under nitrogen protection to prepare a modified additive.

7. The process for the preparation of an antistatic PPO material according to claim 6, characterized in that: The molar ratio of the dimethylvinylsilanol lithium, hexamethylcyclotrisiloxane and Si-Cl bond on the tetrachlorosilane in step B1 is 1:4:

1.

8. The process for the preparation of an antistatic PPO material according to claim 6, characterized in that: The molar ratio of the polysiloxane and thioglycerol in step B2 is 1:

4.

9. The process for the preparation of an antistatic PPO material according to claim 6, characterized in that: The ratio of the pretreated polysiloxane, p-aminobenzoic acid and 4A molecular sieve in step B3 is 10 mmol:40 mmol:7 g.

10. An antistatic PPO material, characterized in that: Prepared according to the preparation method of any one of claims 1-9. Prepared according to the preparation method of any one of claims 1-9.

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