Preparation method of narrow molecular weight distribution oligomeric polyphenyl ether and high-frequency high-speed resin thereof

Abstract

The invention belongs to the technical field of materials and chemical synthesis, and discloses narrow molecular weight distribution oligomeric polyphenyl ether and a preparation method of high-frequency high-speed resin thereof. The preparation method of the narrow molecular weight distribution oligomeric polyphenyl ether comprises the following steps: uniformly stirring phenol and a solvent, and adding a catalyst and a ligand; under the reaction liquid level, introducing gas for bubbling, stirring and reacting, stopping introducing the gas after the reaction is finished, adding an additive, stirring, pouring an excessive solvent, stirring, and separating out a solid. And filtering, taking a filter cake, washing with a solvent, and drying to obtain the narrow molecular weight distribution oligomeric polyphenyl ether. And preparing high-frequency and high-speed resin: mixing the terminated narrow molecular weight distribution oligomeric polyphenyl ether, a solvent and an initiator, stirring to react, pouring into an excessive solvent after the reaction is finished, stirring, and separating out a solid. And filtering, washing a filter cake with a solvent, and drying to obtain the high-frequency high-speed resin. The method realizes efficient preparation of oligomeric polyphenyl ether with narrow molecular weight distribution, is applied to preparation of high-frequency and high-speed resin, and has a good industrial application prospect.

Description

Technical Field

[0001] This invention belongs to the fields of materials and chemical technology, specifically relating to a method for preparing narrow molecular weight distribution oligomeric polyphenylene ethers and their high-frequency and high-speed resins. Background Technology

[0002] High-frequency and high-speed resins are a class of special polymer matrix materials designed and developed specifically to meet the operational requirements of high-frequency (typically referring to the millimeter-wave band of 5G / 6G, >24GHz) and high-speed (data transmission rate >10Gbps) electronic circuits, serving as the "invisible pillar" of modern information infrastructure. With the development of 5G / 6G communication, artificial intelligence, high-performance computing, and autonomous driving, signal frequencies are increasing and transmission rates are accelerating. Traditional circuit board substrates exhibit fatal flaws under high-speed and high-frequency conditions: high dielectric loss (Df), high and unstable dielectric constant (Dk), high hygroscopicity, and poor thermal stability. Therefore, minimizing signal loss, maintaining signal integrity, and providing excellent reliability and processability at extremely high frequencies and data rates is the core mission and key challenge of high-frequency and high-speed resin development.

[0003] Oligomeric polyphenylene ethers (PPEs) refer to polyphenylene ether polymers with low degree of polymerization (n) and relatively small molecular weight, and are a crucial member of the PPE family. With their excellent solubility, low viscosity, high reactivity, and designable end-group functional groups, they play a core role as "performance enhancers" and "bridging molecules" in fields such as high-performance polymer modification, advanced composite materials, and electronic and electrical insulation materials. Among them, narrow molecular weight distribution PPEs can effectively improve the processability, flowability, optical transparency, mechanical properties, thermal stability, and dimensional stability of corresponding resin materials. However, efficient preparation methods for narrow molecular weight distribution PPEs remain highly challenging and require urgent solutions (Journal of Guangdong University of Petrochemical Technology, 2024, 34, 15-24). Summary of the Invention

[0004] To address the challenges of the prior art, the present invention aims to provide a method for preparing narrow molecular weight distribution oligomeric polyphenylene ethers and their high-frequency, high-speed resins.

[0005] The objective of this invention is achieved through the following technical solution: This invention provides a method for preparing narrow molecular weight distribution oligomeric polyphenylene ethers, comprising the following steps: Phenol and solvent are added to a dry, clean flask equipped with a magnetic stirrer or mechanical stirrer. After the reaction system is stirred evenly, the catalyst and ligand are added. Gas is bubbled through the mixture at a certain flow rate below the surface of the reaction liquid. The reaction system is stirred and reacted for a certain time at a certain temperature. After the reaction is completed, the gas flow is stopped, a certain amount of additive is added, and the mixture is stirred for a certain time. The resulting mixed solution is poured into an excess of solvent and stirred, causing a solid to precipitate. The solid is filtered, and the filter cake is washed with a certain amount of solvent. The resulting filter cake is dried to obtain a narrow molecular weight distribution oligomeric polyphenylene ether.

[0006] Preferably, the phenol is phenol, propofol, 2,6-dimethylphenol, 2,6-diphenylphenol, 2,6-dichlorophenol, 2,6-dibromophenol, 2,5-dimethylphenol, 2,5-diphenylphenol, 2,5-dichlorophenol, 2,5-dibromophenol, o-cresol, resorcinol, hydroquinone, tris(triphenylphenol), triclosan, bromocresol green, 4,4′,4′′,4′′′-(ethylene-1,1,2,2-tetramethyl)tetraphenol, 4,4′-(1,2-diphenylethylene-1,2-dimethyl)diphenol, 4,4'-(ethylene-1,2-dimethyl)diphenol, bisphenol A, bisphenol A-D16, tetrabromobisphenol A, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxy One or more of the following: diphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfone, 4,4'-thiobis(6-tert-butyl-m-cresol), 9,9-bis(3-methyl-4-hydroxyphenyl)fluorene, tetrachlorobisphenol A, tetramethylbisphenol A, bisphenol B, bisphenol C, bisphenol AP, tetrabromobisphenol S, bisphenol S, bisphenol Z, 2,2-bis(4-hydroxyphenyl)propane-methyl-D6, bisphenol A-2,2',6,6'-D4, bisphenol F-D10, 4,4'-diphenylmethylene bisphenol, 2,2'-dihydroxybenzophenone, 2,2'-dihydroxybenzane, 2,2'-binaphthol, 2,2'-biphenyl, 4,4'-biphenyl, spirocyclodiol, and 4,4'-(hexafluoroisopropylidene)bisphenol.

[0007] Preferably, the catalyst is one or more of the following: copper chloride, copper bromide, copper oxide, copper acetate, copper sulfate, copper nitrate, copper trifluoromethanesulfonate, basic copper carbonate, copper hydroxide, cuprous chloride, cuprous oxide, ketone bromide, cuprous iodide, cuprous trifluoromethanesulfonate, cuprous acetonitrile tetrafluoroborate, cuprous acetonitrile hexafluorophosphate, cobalt chloride, ferric chloride, ferric bromide, ferrous chloride, ferrous bromide, ferrous sulfate, iron(II,III) oxide, ferric sulfate, nickel chloride, nickel bromide, and nickel acetate.

[0008] Preferably, the ligand is pyridine, 2-chloropyridine, 2-methylpyridine, 3-acetylpyridine, 2,6-difluoropyridine, 2,6-dichloropyridine, 2,3-dichloro-5-trifluoromethylpyridine, 2-aminomethylpyridine, 2-aminopyridine, 2,6-tert-butylpyridine, 2-hydroxypyridine, bipyridine, α,α,α-tert-pyridine, 4-methoxy-2-methylpyridine, propylamine, isopropylamine, n-butylamine, tert-butylamine, pentylamine, or hexylamine. Cyclopropane, cyclobutylamine, cyclopentylamine, cyclohexylamine, aniline, benzylamine, 4-chloroaniline, 4-methylaniline, 4-methoxyaniline, 4-bromoaniline, 4-tert-butylaniline, 3-chloroaniline, 3-methylaniline, 3-methoxyaniline, 3-bromoaniline, 3-tert-butylaniline, 2-chloroaniline, 2-methylaniline, 2-methoxyaniline, 2-bromoaniline, 2-tert-butylaniline, urea, di-n-butylamine, diisopropylamine, cyclohexanediamine, N One or more of the following: -methylbenzylamine, triphenylphosphine, BINAP, tricyclohexylphosphine, and tri-tert-butylphosphine.

[0009] Preferably, the solvent is toluene, benzene, xylene, diethyl ether, tetrahydrofuran, methyl tert-butyl ether, methanol, ethanol, isopropanol, trifluoroethanol, hexafluoroisopropanol, butanol, acetonitrile, dichloromethane, 1,2-dichloroethane, 1,4-dioxane, acetic acid, ethyl acetate, butyl acetate, amyl acetate, dimethyl sulfoxide, etc. N , N -Dimethylformamide, N One or more of methylpyrrolidone and methyl ethyl ketone.

[0010] Preferably, the introduced gas is one or more of oxygen, air and nitrogen.

[0011] Preferably, the reaction temperature is 0–110°C.

[0012] Preferably, the additive is one or more of acetic acid, ethylenediamine, aminotriacetic acid, disodium ethylenediaminetetraacetate, and sodium diethyldithiocarbamate.

[0013] The present invention also provides a narrow molecular weight distribution oligomeric polyphenylene ether, which is prepared by the above preparation method and has a number average molecular weight of 600~2000.

[0014] This invention also provides a method for preparing a high-frequency, high-speed resin, comprising the following steps: (1) End capping of narrow molecular weight distribution oligopolyphenylene ether In a dry, clean flask equipped with a magnetic stirrer or mechanical stirrer, add narrow molecular weight distribution oligopolyphenylene ether, solvent, base, and end-capping reagent. Stir the reaction system at a specific temperature for a certain time. After the reaction is complete, pour the resulting mixture into an excess of solvent and stir, causing a solid to precipitate. Filter the mixture, wash the filter cake with a certain amount of solvent, and dry the resulting filter cake to obtain end-capped narrow molecular weight distribution oligopolyphenylene ether.

[0015] (2) Preparation of high-frequency and high-speed resins In a dry, clean flask equipped with a magnetic stirrer or mechanical stirrer, add end-capped, narrow molecular weight distribution oligomeric polyphenylene ether, solvent, and initiator. At a specific temperature, stir the reaction system for a certain time. After the reaction is complete, pour the resulting mixed solution into an excess of solvent and stir, causing a solid to precipitate. Filter the solution, wash the filter cake with a certain amount of solvent, and dry the resulting filter cake to obtain a high-frequency, high-speed resin.

[0016] Preferably, in step (1), the base is one or more of lithium fluoride, potassium fluoride, potassium carbonate, sodium carbonate, lithium carbonate, sodium bicarbonate, sodium phosphate, potassium phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, cesium carbonate, sodium hydroxide, lithium hydroxide, potassium hydroxide, cesium hydroxide, calcium hydroxide, magnesium hydroxide, lithium tert-butoxide, sodium tert-butoxide, potassium tert-butoxide, sodium methoxide, potassium methoxide, sodium ethoxide, triethylamine, diisopropylethylamine, 1,8-diazabicyclo[5.4.0]undec-7-ene, triethylenediamine, and pyridine.

[0017] Preferably, in step (1), the capping reagent is α-methacrylic acid, α-methacrylic anhydride, α-methacryloyl chloride, α-methacryloyl bromide, α-ethylacrylic acid, α-ethylacrylic anhydride, α-ethylacryloyl chloride, α-propylacrylic acid, α-propylacrylic anhydride, α-propylacryloyl chloride, α-propylacryloyl bromide, α-cyclopropylacrylic acid, α-cyclopropylacrylic anhydride, α-cyclopropylacryloyl chloride, α-cyclopropylacryloyl bromide, α-phenylacrylic acid, α-phenylacrylic anhydride, α-phenylacrylic anhydride, α-phenylacrylic acid. One or more of the following: acryloyl chloride, α-phenylacryloyl bromide, vinyl phosphoric acid, vinyl linyl chloride, acrylic acid, acrylic anhydride, acryloyl chloride, acryloyl bromide, 4-vinylbenzoic acid, 4-vinylbenzoic anhydride, 4-vinylbenzoyl chloride, 4-vinylbenzoyl bromide, 4-(acrylamide)benzoic acid, 4-vinyltetrafluorophenylacetic acid, 4-vinyltetrafluorophenylacetic anhydride, 4-vinyltetrafluorophenylacetyl chloride, and 4-vinyltetrafluorophenylacetyl bromide, wherein the molar ratio of narrow molecular weight distribution oligophenyl ether to end-capping reagent is 1:2 to 1:4.

[0018] Preferably, in step (2), the initiator is one or more of the following: benzoyl peroxide, di-tert-butyl peroxide, dicumyl peroxide, tert-butyl peroxide, dodecyl peroxide, azobisisobutyronitrile, azobisisobutyronitrile, azobisisobutyramidoline, azobisisobutyramidine hydrochloride, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, benzophenone, benzoin dimethyl ether, isopropylthioxanthrone, potassium persulfate, ammonium persulfate, and sodium persulfate.

[0019] Preferably, in steps (1) and (2), the solvent is toluene, benzene, xylene, diethyl ether, tetrahydrofuran, methyl tert-butyl ether, methanol, ethanol, isopropanol, trifluoroethanol, hexafluoroisopropanol, butanol, acetonitrile, dichloromethane, 1,2-dichloroethane, 1,4-dioxane, acetic acid, ethyl acetate, butyl acetate, amyl acetate, dimethyl sulfoxide, etc. N , N -Dimethylformamide, N One or more of methylpyrrolidone and methyl ethyl ketone. Preferably, the reaction temperature is 0–110°C.

[0020] The present invention also provides a high-frequency, high-speed resin, which is prepared by the above-described preparation method.

[0021] The preparation method of the present invention has the following advantages: (1) The method for preparing narrow molecular weight distribution oligopolyphenylene ether provided by the present invention achieves efficient preparation of narrow molecular weight distribution oligopolyphenylene ether.

[0022] (2) The narrow molecular weight distribution oligopolyphenylene ether of the present invention can be used to prepare high-frequency and high-speed resins and has good industrial application prospects. Attached Figure Description

[0023] Figure 1 These are gel permeation chromatography (GPC) results of the narrow molecular weight distribution oligophenyl ethers obtained in Examples 1-10.

[0024] Figure 2 These are the 1H NMR spectra of the narrow molecular weight distribution oligophenyl ethers obtained in Examples 1-10. Detailed Implementation

[0025] The present invention will be further described in detail below with reference to the embodiments and accompanying drawings, but the embodiments of the present invention are not limited thereto.

[0026] Preparation of narrow molecular weight distribution oligomeric polyphenylene ethers: Example 1 In a dry, clean flask equipped with a magnetic stirrer, add 40 mmol of o-cresol, 10 mmol of bisphenol A, 20 mL of toluene, and 4 mL of methanol. After the reaction system is thoroughly stirred, add 1 mmol of cuprous chloride and 1.2 mmol of n-butylamine. Bubble oxygen through the mixture at a flow rate of 5 mL / min below the surface of the reaction liquid. Stir the reaction system at 0 °C for 1 hour. After the reaction is complete, stop the gas flow and add 1 mmol of acetic acid and 1 mmol of disodium ethylenediaminetetraacetate. After stirring for 1 hour, pour the resulting mixture into 300 mL of isopropanol and stir, precipitating a solid. Filter the solid, wash the filter cake with 20 mL of isopropanol, and dry the filter cake to obtain a narrow molecular weight distribution oligomeric polyphenylene ether with a yield of 72% and a number average molecular weight M. n = 996, weight-average molecular weight Mw = 1361, polymer dispersibility index PDI = 1.409.

[0027] Example 2 In a dry, clean flask equipped with a magnetic stirrer, add 40 mmol of 2,6-dimethylphenol, 10 mmol of tetramethylbisphenol A, 20 mL of xylene, and 4 mL of isopropanol. After the reaction system is thoroughly stirred, add 1 mmol of cuprous bromide and 1.2 mmol of pyridine. Bubbling oxygen is introduced at a flow rate of 10 mL / min below the surface of the reaction liquid. The reaction system is stirred at 40 °C for 3 hours. After the reaction is complete, the gas flow is stopped, and 1 mmol of acetic acid and 1 mmol of disodium ethylenediaminetetraacetate are added. After stirring for 1 hour, the resulting mixture is poured into 300 mL of methanol and stirred, precipitating a solid. Filter the mixture, wash the filter cake with 20 mL of methanol, and dry the filter cake to obtain a narrow molecular weight distribution oligomeric polyphenylene ether with a yield of 85%. n = 1071, M w =1491, PDI = 1.317.

[0028] Example 3 In a dry, clean flask equipped with a magnetic stirrer, add 40 mmol of 2,6-dimethylphenol, 10 mmol of tetramethylbisphenol A, 20 mL of toluene, and 4 mL of ethanol. After the reaction system is thoroughly stirred, add 1 mmol of copper acetate and 1.2 mmol of aniline. Bubble oxygen through the mixture at a flow rate of 10 mL / min below the surface of the reaction liquid. Stir the reaction system at 40 °C for 3 hours. After the reaction is complete, stop the gas flow and add 1 mmol of acetic acid and 1 mmol of disodium ethylenediaminetetraacetate. After stirring for 1 hour, pour the resulting mixture into 300 mL of methanol and stir, precipitating a solid. Filter the mixture, wash the filter cake with 20 mL of methanol, and dry the filter cake to obtain a narrow molecular weight distribution oligomeric polyphenylene ether with a yield of 71%. n = 660, M w = 853, PDI = 1.293.

[0029] Example 4 In a dry, clean flask equipped with a magnetic stirrer, add 40 mmol of 2,6-dimethylphenol, 10 mmol of tetrabromobisphenol S, 20 mL of toluene, and 4 mL of 1,4-dioxane. After the reaction system is thoroughly stirred, add 1 mmol of copper acetate and 1.2 mmol of aniline. Blow oxygen through the mixture at a flow rate of 10 mL / min below the surface of the reaction liquid. Stir the reaction system at 40 °C for 3 hours. After the reaction is complete, stop the gas flow and add 1 mmol of acetic acid and 1 mmol of disodium ethylenediaminetetraacetate. After stirring for 1 hour, pour the resulting mixture into 300 mL of methanol and stir, precipitating a solid. Filter the mixture, wash the filter cake with 20 mL of methanol, and dry the filter cake to obtain a narrow molecular weight distribution oligomeric polyphenylene ether with a yield of 71%. n = 1153, M w =1580, PDI = 1.370.

[0030] Example 5 In a dry, clean flask equipped with a magnetic stirrer, add 40 mmol of 2,6-dimethylphenol, 10 mmol of bisphenol AP, 20 mL of toluene, and 4 mL of butanol. After the reaction system is thoroughly stirred, add 1 mmol of copper acetate and 1.2 mmol of aniline. Bubble air through the mixture at a flow rate of 10 mL / min below the surface of the reaction liquid. Stir the reaction system at 110 °C for 3 hours. After the reaction is complete, stop the gas flow and add 1 mmol of acetic acid and 1 mmol of disodium ethylenediaminetetraacetate. After stirring for 1 hour, pour the resulting mixture into 300 mL of methanol and stir to precipitate a solid. Filter the solid, wash the filter cake with 20 mL of methanol, and dry the filter cake to obtain a narrow molecular weight distribution oligomeric polyphenylene ether with a yield of 12%. n = 642, M w = 954, PDI = 1.485.

[0031] Example 6 In a dry, clean flask equipped with a magnetic stirrer, add 40 mmol of 2,6-dimethylphenol, 10 mmol of tetramethylbisphenol A, and 20 mL of toluene. After the reaction system is thoroughly stirred, add 1 mmol of cuprous chloride, 1.2 mmol of pyridine, and 1.2 mmol of di-n-butylamine. Bubbling oxygen is introduced at a flow rate of 10 mL / min below the surface of the reaction liquid. The reaction system is stirred at 40 °C for 3 hours. After the reaction is complete, the gas flow is stopped, and 1 mmol of acetic acid and 1 mmol of disodium ethylenediaminetetraacetate are added. After stirring for 1 hour, the resulting mixture is poured into 300 mL of methanol and stirred, precipitating a solid. Filter the mixture, wash the filter cake with 20 mL of methanol, and dry the filter cake to obtain a narrow molecular weight distribution oligomeric polyphenylene ether with a yield of 99%. n = 1822, M w =2364, PDI = 1.296.

[0032] Example 7 In a dry, clean flask equipped with a magnetic stirrer, add 40 mmol of 2,6-dimethylphenol, 10 mmol of tetramethylbisphenol S, 20 mL of toluene, and 4 mL of trifluoroethanol. After the reaction system is thoroughly stirred, add 1 mmol of ferric chloride, 1.2 mmol of 2-chloropyridine, and 1.2 mmol of cyclohexanediamine. Bubbling oxygen is introduced at a flow rate of 10 mL / min below the surface of the reaction liquid. The reaction system is stirred at 40 °C for 3 hours. After the reaction is complete, the gas flow is stopped, and 1 mmol of acetic acid and 1 mmol of disodium ethylenediaminetetraacetate are added. After stirring for 1 hour, the resulting mixture is poured into 300 mL of methanol and stirred, precipitating a solid. Filter the mixture, wash the filter cake with 20 mL of methanol, and dry the filter cake to obtain a narrow molecular weight distribution oligomeric polyphenylene ether with a yield of 99%. n = 1799, M w = 3373, PDI = 1.875.

[0033] Example 8 In a dry, clean flask equipped with a magnetic stirrer, add 40 mmol of 2,6-diphenylphenol, 10 mmol of tetramethylbisphenol S, 20 mL of toluene, and 4 mL of acetonitrile. After the reaction system is thoroughly stirred, add 1 mmol of ferric chloride, 1.2 mmol of 2-chloropyridine, and 1.2 mmol of cyclohexanediamine. Bubbling oxygen is introduced at a flow rate of 10 mL / min below the surface of the reaction liquid. The reaction system is stirred at 40 °C for 3 hours. After the reaction is complete, the gas flow is stopped, and 1 mmol of acetic acid and 1 mmol of disodium ethylenediaminetetraacetate are added. After stirring for 1 hour, the resulting mixture is poured into 300 mL of methanol and stirred, precipitating a solid. Filter the mixture, wash the filter cake with 20 mL of diethyl ether, and dry the filter cake to obtain a narrow molecular weight distribution oligomeric polyphenylene ether with a yield of 91%. n = 1591, M w = 2042, PDI = 1.283.

[0034] Example 9 In a dry, clean flask equipped with a magnetic stirrer, add 40 mmol of 2,6-diphenylphenol, 10 mmol of tetramethylbisphenol S, 20 mL of toluene, and 4 mL of acetonitrile. After the reaction system is thoroughly stirred, add 1 mmol of ferric chloride, 1.2 mmol of bipyridine, and 1.2 mmol of triphenylphosphine. Bubbling oxygen is introduced at a flow rate of 10 mL / min below the surface of the reaction liquid. The reaction system is stirred at 60 °C for 3 hours. After the reaction is complete, the gas flow is stopped, and 1 mmol of acetic acid and 1 mmol of disodium ethylenediaminetetraacetate are added. After stirring for 1 hour, the resulting mixture is poured into 300 mL of methanol and stirred, precipitating a solid. Filter the mixture, wash the filter cake with 20 mL of methanol, and dry the filter cake to obtain a narrow molecular weight distribution oligomeric polyphenylene ether with a yield of 26%. n =1119, M w = 1416, PDI = 1.265.

[0035] Example 10 In a dry, clean flask equipped with a magnetic stirrer, add 40 mmol of 2,6-diphenylphenol, 10 mmol of tetramethylbisphenol S, 20 mL of toluene, and 4 mL of acetonitrile. After the reaction system is thoroughly stirred, add 1 mmol of nickel bromide, 1.2 mmol of bipyridine, and 1.2 mmol of triphenylphosphine. Bubbling oxygen is introduced at a flow rate of 10 mL / min below the surface of the reaction liquid. The reaction system is stirred at 60 °C for 3 hours. After the reaction is complete, the gas flow is stopped, and 1 mmol of acetic acid and 1 mmol of disodium ethylenediaminetetraacetate are added. After stirring for 1 hour, the resulting mixture is poured into 300 mL of methanol and stirred, precipitating a solid. Filter the mixture, wash the filter cake with 20 mL of methanol, and dry the filter cake to obtain a narrow molecular weight distribution oligomeric polyphenylene ether with a yield of 52%. n =1433, M w = 2277, PDI = 1.588.

[0036] Figure 1 The gel permeation chromatography (GPC) results of the narrow molecular weight distribution oligophenyl ethers obtained in Examples 1-10 are shown.

[0037] Figure 2 The results of 1H NMR spectroscopy of the narrow molecular weight distribution oligophenyl ethers obtained in Examples 1-10 are shown.

[0038] End-capping of narrow molecular weight distribution oligomeric polyphenylene ethers: Example 11 In a dry, clean flask equipped with a magnetic stirrer or mechanical stirrer, add 10 mmol of the narrow molecular weight distribution oligopolyphenylene ether prepared in Example 6, 20 mL of toluene, 20 mmol of triethylamine, and 20 mmol of α-methacryloyl chloride. The reaction system is stirred at 30 °C for 4 hours. After the reaction is complete, the resulting mixture is poured into 300 mL of methanol and stirred, causing a solid to precipitate. The solid is filtered, and the filter cake is washed with 30 mL of methanol. The resulting filter cake is dried to obtain the end-capped narrow molecular weight distribution oligopolyphenylene ether, with a yield of 97%.

[0039] Example 12 In a dry, clean flask equipped with a magnetic stirrer or mechanical stirrer, add 10 mmol of the narrow molecular weight distribution oligopolyphenylene ether prepared in Example 7, 20 mL of dichloromethane, 20 mmol of potassium carbonate, and 20 mmol of α-methacryloyl chloride. The reaction system is stirred at 10 °C for 4 hours. After the reaction is complete, the resulting mixture is poured into 300 mL of methanol and stirred, causing a solid to precipitate. The solid is filtered, and the filter cake is washed with 30 mL of methanol. The resulting filter cake is dried to obtain the end-capped narrow molecular weight distribution oligopolyphenylene ether, with a yield of 65%.

[0040] Example 13 In a dry, clean flask equipped with a magnetic stirrer or mechanical stirrer, add 10 mmol of the narrow molecular weight distribution oligopolyphenylene ether prepared in Example 6, 20 mL of tetrahydrofuran, 20 mmol of triethylenediamine, and 20 mmol of α-phenylacryloyl chloride. The reaction system is stirred at 30 °C for 4 hours. After the reaction is complete, the resulting mixture is poured into 300 mL of methanol and stirred, causing a solid to precipitate. The solid is filtered, and the filter cake is washed with 30 mL of methanol. The resulting filter cake is dried to obtain the end-capped narrow molecular weight distribution oligopolyphenylene ether, with a yield of 99%.

[0041] Example 14 In a dry, clean flask equipped with a magnetic stirrer or mechanical stirrer, add 10 mmol of the narrow molecular weight distribution oligopolyphenylene ether prepared in Example 6, 20 mL of methyl tert-butyl ether, 40 mmol of sodium bicarbonate, and 20 mmol of acrylic anhydride. The reaction system is stirred at 30 °C for 4 hours. After the reaction is complete, the resulting mixture is poured into 300 mL of methanol and stirred, causing a solid to precipitate. The solid is filtered, and the filter cake is washed with 30 mL of methanol. The resulting filter cake is dried to obtain the end-capped narrow molecular weight distribution oligopolyphenylene ether, with a yield of 69%.

[0042] Example 15 Add 10 mmol of the narrow molecular weight distribution oligopolyphenylene ether prepared in Example 6 and 20 mL of [unspecified substance] to a dry, clean flask equipped with a magnetic stirrer or mechanical stirrer. N,N-Dimethylformamide, 80 mmol sodium methoxide, and 20 mmol α-cyclopropylacryloyl bromide were reacted. The reaction system was stirred at 30 °C for 4 hours. After the reaction was completed, the resulting mixture was poured into 300 mL of isopropanol and stirred, resulting in the precipitation of a solid. The solid was filtered, and the filter cake was washed with 30 mL of isopropanol. The resulting filter cake was dried to obtain a capped narrow molecular weight distribution oligomeric polyphenylene ether with a yield of 69%.

[0043] Example 16 In a dry, clean flask equipped with a magnetic stirrer or mechanical stirrer, add 10 mmol of the narrow molecular weight distribution oligopolyphenylene ether prepared in Example 6, 20 mL of methyl tert-butyl ether, 20 mmol of sodium bicarbonate, and 20 mmol of α-phenylacrylic acid. The reaction system is stirred at 65 °C for 2 hours. After the reaction is complete, the resulting mixture is poured into 300 mL of methanol and stirred, causing a solid to precipitate. The solid is filtered, and the filter cake is washed with 30 mL of methanol. The resulting filter cake is dried to obtain end-capped narrow molecular weight distribution oligopolyphenylene ether, with a yield of 8%.

[0044] Example 17 In a dry, clean flask equipped with a magnetic stirrer or mechanical stirrer, add 10 mmol of the narrow molecular weight distribution oligopolyphenylene ether prepared in Example 6, 20 mL of dimethyl sulfoxide, 20 mmol of potassium phosphate, and 20 mmol of 4-vinylbenzoyl chloride. The reaction system is stirred at 110 °C for 2 hours. After the reaction is complete, the resulting mixture is poured into 300 mL of methanol and stirred, causing a solid to precipitate. The solid is filtered, and the filter cake is washed with 30 mL of methanol. The resulting filter cake is dried to obtain the end-capped narrow molecular weight distribution oligopolyphenylene ether, with a yield of 85%.

[0045] Example 18 In a dry, clean flask equipped with a magnetic stirrer or mechanical stirrer, add 10 mmol of the narrow molecular weight distribution oligopolyphenylene ether prepared in Example 6, 20 mL of 1,2-dichloroethane, 20 mmol of pyridine, and 20 mmol of 4-vinylbenzoyl chloride. The reaction system is stirred at 65 °C for 2 hours. After the reaction is complete, the resulting mixture is poured into 300 mL of methanol and stirred, causing a solid to precipitate. The solid is filtered, and the filter cake is washed with 30 mL of methanol. The resulting filter cake is dried to obtain the end-capped narrow molecular weight distribution oligopolyphenylene ether, with a yield of 96%.

[0046] Preparation of high-frequency and high-speed resins: Example 19 In a dry, clean flask equipped with a magnetic stirrer or mechanical stirrer, add 10 mmol of the end-capped narrow molecular weight distribution oligophenyl ether prepared in Example 13, 20 mL of methyl ethyl ketone, and 0.5 mmol of benzoyl peroxide. The reaction system was stirred at 80 °C for 3 hours. After the reaction was complete, the resulting mixture was poured into 300 mL of methanol and stirred, resulting in the precipitation of a solid. The solid was filtered, and the filter cake was washed with 30 mL of methanol. After drying, the resulting high-frequency, high-speed resin was obtained with a yield of 96%, a dielectric constant of 2.54 (1 MHz), and a dielectric loss of 0.0007.

[0047] Example 20 In a dry, clean flask equipped with a magnetic stirrer or mechanical stirrer, add 10 mmol of the end-capped narrow molecular weight distribution oligophenyl ether prepared in Example 13, 20 mL of methyl ethyl ketone, and 0.5 mmol of benzoyl peroxide. The reaction system was stirred at 80 °C for 3 hours. After the reaction was complete, the resulting mixture was poured into 300 mL of methanol and stirred, resulting in the precipitation of a solid. The solid was filtered, and the filter cake was washed with 30 mL of methanol. After drying, the resulting high-frequency, high-speed resin was obtained with a yield of 96%, a dielectric constant of 2.54 (1 MHz), and a dielectric loss of 0.0007.

[0048] Example 21 In a dry, clean flask equipped with a magnetic stirrer or mechanical stirrer, add 10 mmol of the end-capped narrow molecular weight distribution oligophenyl ether prepared in Example 13, 20 mL of methyl ethyl ketone, and 0.5 mmol of azobisisobutyronitrile. The reaction system was stirred at 70 °C for 3 hours. After the reaction was complete, the resulting mixture was poured into 300 mL of methanol and stirred, resulting in the precipitation of a solid. The solid was filtered, and the filter cake was washed with 30 mL of isopropanol. After drying, the resulting high-frequency, high-speed resin was obtained with a yield of 95%, a dielectric constant of 2.54 (1 MHz), and a dielectric loss of 0.0007.

[0049] Example 22 In a dry, clean flask equipped with a magnetic stirrer or mechanical stirrer, add 10 mmol of the end-capped narrow molecular weight distribution oligophenyl ether prepared in Example 13, 20 mL of methyl ethyl ketone, and 0.5 mmol of ammonium persulfate. The reaction system was stirred at 150 °C for 3 hours. After the reaction was complete, the resulting mixture was poured into 300 mL of methanol and stirred, resulting in the precipitation of a solid. The solid was filtered, and the filter cake was washed with 30 mL of isopropanol. The resulting filter cake was dried to obtain a high-frequency, high-speed resin with a yield of 56%, a dielectric constant of 2.54 (1 MHz), and a dielectric loss of 0.0007.

[0050] Example 23 In a dry, clean flask equipped with a magnetic stirrer or mechanical stirrer, add 10 mmol of the end-capped narrow molecular weight distribution oligophenyl ether prepared in Example 13, 20 mL of methyl ethyl ketone, and 0.5 mmol of dicumyl peroxide. The reaction system was stirred at 280 °C for 4 hours. After the reaction was complete, the resulting mixture was poured into 300 mL of methanol and stirred, causing a solid to precipitate. The solid was filtered, and the filter cake was washed with 30 mL of isopropanol. The resulting filter cake was dried to obtain a high-frequency, high-speed resin with a yield of 96%, a dielectric constant of 2.54 (1 MHz), and a dielectric loss of 0.0007.

[0051] In summary, the narrow molecular weight distribution oligopolyphenylene ether prepared by this invention has a narrow molecular weight distribution and can be used to prepare high-frequency and high-speed resins.

[0052] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. A method for preparing a narrow molecular weight distribution oligomeric polyphenylene ether, characterized in that, Includes the following steps: Phenol and solvent were stirred evenly, catalyst and ligand were added, gas was bubbled under the liquid surface and stirred to react. After the reaction was completed, gas was stopped, additives were added and stirred, and then poured into excess solvent and stirred to precipitate solid. The solid was filtered, and the filter cake was washed with solvent. The obtained filter cake was dried to obtain narrow molecular weight distribution oligomeric polyphenylene ether.

2. The method for preparing a narrow molecular weight distribution oligomeric polyphenylene ether according to claim 1, characterized in that, The phenol is phenol, propofol, 2,6-dimethylphenol, 2,6-diphenylphenol, 2,6-dichlorophenol, 2,6-dibromophenol, 2,5-dimethylphenol, 2,5-diphenylphenol, 2,5-dichlorophenol, 2,5-dibromophenol, o-cresol, resorcinol, hydroquinone, tris(triphenylphenol), triclosan, bromocresol green, 4,4′,4′′,4′′′-(ethylene-1,1,2,2-tetramethyl)tetraphenol, 4,4′-(1,2-diphenylethylene-1,2-dimethyl)diphenol, 4,4'-(ethylene-1,2-dimethyl)diphenol, bisphenol A, bisphenol A-D16, tetrabromobisphenol A, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfide, etc. One or more of the following: benzene sulfoxide, 4,4'-dihydroxydiphenyl sulfone, 4,4'-thiobis(6-tert-butyl-m-cresol), 9,9-bis(3-methyl-4-hydroxyphenyl)fluorene, tetrachlorobisphenol A, tetramethylbisphenol A, bisphenol B, bisphenol C, bisphenol AP, tetrabromobisphenol S, bisphenol S, bisphenol Z, 2,2-bis(4-hydroxyphenyl)propane-methyl-D6, bisphenol A-2,2',6,6'-D4, bisphenol F-D10, 4,4'-diphenylmethylene bisphenol, 2,2'-dihydroxybenzophenone, 2,2'-dihydroxybenzane, 2,2'-binaphthol, 2,2'-biphenyl, 4,4'-biphenyl, spirocyclodiol, and 4,4'-(hexafluoroisopropylidene)bisphenol.

3. The method for preparing a narrow molecular weight distribution oligomeric polyphenylene ether according to claim 1, characterized in that, The catalyst is one or more of the following: copper chloride, copper bromide, copper oxide, copper acetate, copper sulfate, copper nitrate, copper trifluoromethanesulfonate, basic copper carbonate, copper hydroxide, cuprous chloride, cuprous oxide, cuprous bromide, cuprous iodide, cuprous trifluoromethanesulfonate, cuprous acetonitrile tetrafluoroborate, cuprous acetonitrile hexafluorophosphate, cobalt chloride, ferric chloride, ferric bromide, ferrous chloride, ferrous bromide, ferrous sulfate, iron(II,III) oxide, ferric sulfate, nickel chloride, nickel bromide, and nickel acetate.

4. The method for preparing a narrow molecular weight distribution oligomeric polyphenylene ether according to claim 1, characterized in that, The ligands are pyridine, 2-chloropyridine, 2-methylpyridine, 3-acetylpyridine, 2,6-difluoropyridine, 2,6-dichloropyridine, 2,3-dichloro-5-trifluoromethylpyridine, 2-aminomethylpyridine, 2-aminopyridine, 2,6-tert-butylpyridine, 2-hydroxypyridine, bipyridine, α,α,α-tert-pyridine, 4-methoxy-2-methylpyridine, propylamine, isopropylamine, n-butylamine, tert-butylamine, pentylamine, and hexylamine. Cyclopropane, cyclobutylamine, cyclopentylamine, cyclohexylamine, aniline, benzylamine, 4-chloroaniline, 4-methylaniline, 4-methoxyaniline, 4-bromoaniline, 4-tert-butylaniline, 3-chloroaniline, 3-methylaniline, 3-methoxyaniline, 3-bromoaniline, 3-tert-butylaniline, 2-chloroaniline, 2-methylaniline, 2-methoxyaniline, 2-bromoaniline, 2-tert-butylaniline, urea, di-n-butylamine, diisopropylamine, cyclohexanediamine, N One or more of the following: -methylbenzylamine, triphenylphosphine, BINAP, tricyclohexylphosphine, and tri-tert-butylphosphine.

5. The method for preparing a narrow molecular weight distribution oligomeric polyphenylene ether according to claim 1, characterized in that, The solvent is toluene, benzene, xylene, diethyl ether, tetrahydrofuran, methyl tert-butyl ether, methanol, ethanol, isopropanol, trifluoroethanol, hexafluoroisopropanol, butanol, acetonitrile, dichloromethane, 1,2-dichloroethane, 1,4-dioxane, acetic acid, ethyl acetate, butyl acetate, amyl acetate, dimethyl sulfoxide, etc. N , N -Dimethylformamide, N One or more of methylpyrrolidone and methyl ethyl ketone; the introduced gas is one or more of oxygen, air and nitrogen; the reaction temperature is 0-280℃; the additive is one or more of acetic acid, ethylenediamine, aminotriacetic acid, disodium ethylenediaminetetraacetate, and sodium diethyldithiocarbamate.

6. A narrow molecular weight distribution oligomeric polyphenylene ether, characterized in that, The number-average molecular weight is 600-2000, prepared by the preparation method according to any one of claims 1 to 5.

7. A method for preparing a high-frequency, high-speed resin, characterized in that, Includes the following steps: (1) End-capping of narrow molecular weight distribution oligopolyphenylene ethers: The narrow molecular weight distribution oligopolyphenylene ether of claim 6, solvent, alkali and end-capping reagent are stirred and reacted. After the reaction is completed, it is poured into an excess solvent and stirred. The solid is precipitated, filtered, and the filter cake is washed with solvent. The obtained filter cake is dried to obtain the end-capped narrow molecular weight distribution oligopolyphenylene ether. (2) Preparation of high-frequency and high-speed resin: The narrow molecular weight distribution oligomeric polyphenylene ether, solvent and initiator were stirred and reacted. After the reaction was completed, the mixture was poured into an excess of solvent and stirred to precipitate a solid. The solid was filtered, and the filter cake was washed with solvent. The resulting filter cake was dried to obtain a high-frequency high-speed resin.

8. The method for preparing a high-frequency, high-speed resin according to claim 7, characterized in that, In step (1), the alkali is one or more of the following: lithium fluoride, potassium fluoride, potassium carbonate, sodium carbonate, lithium carbonate, sodium bicarbonate, sodium phosphate, potassium phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, cesium carbonate, sodium hydroxide, lithium hydroxide, potassium hydroxide, cesium hydroxide, calcium hydroxide, magnesium hydroxide, lithium tert-butoxide, sodium tert-butoxide, potassium tert-butoxide, sodium methoxide, potassium methoxide, sodium ethoxide, triethylamine, diisopropylethylamine, 1,8-diazabicyclo[5.4.0]undec-7-ene, triethylenediamine, and pyridine. The capping reagent is α-methacrylic acid, α-methacrylic anhydride, α-methacryloyl chloride, α-methacryloyl bromide, α-ethylacrylic acid, α-ethylacrylic anhydride, α-ethylacryloyl chloride, α-propylacrylic acid, α-propylacrylic anhydride, α-propylacryloyl chloride, α-propylacryloyl bromide, α-cyclopropylacrylic acid, α-cyclopropylacrylic anhydride, α-cyclopropylacryloyl chloride, α-cyclopropylacryloyl bromide, α-phenylacrylic acid, α-phenylacrylic anhydride, α-phenylacryloyl chloride, α... One or more of the following: phenylacryloyl bromide, vinyl phosphoric acid, vinyl linoleic chloride, acrylic acid, acrylic anhydride, acryloyl chloride, acryloyl bromide, 4-vinylbenzoic acid, 4-vinylbenzoic anhydride, 4-vinylbenzoyl chloride, 4-vinylbenzoyl bromide, 4-(acrylamide)benzoic acid, 4-vinyltetrafluorophenylacetic acid, 4-vinyltetrafluorophenylacetic anhydride, 4-vinyltetrafluorophenylacetyl chloride, and 4-vinyltetrafluorophenylacetyl bromide, wherein the molar ratio of narrow molecular weight distribution oligophenyl ether to end-capping reagent is 1:2 to 1:

4.

9. The method for preparing a high-frequency, high-speed resin according to claim 7, characterized in that, In step (2), the initiator is one or more of the following: benzoyl peroxide, di-tert-butyl peroxide, dicumyl peroxide, tert-butyl peroxide, dodecyl peroxide, azobisisobutyronitrile, azobisisobutyronitrile, azobisisobutyramidoline, azobisisobutyramidine hydrochloride, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, benzophenone, benzoin dimethyl ether, isopropylthioxanthone, potassium persulfate, ammonium persulfate, and sodium persulfate.

10. The method for preparing a high-frequency, high-speed resin according to claim 7, characterized in that, In steps (1) and (2), the solvent is toluene, benzene, xylene, diethyl ether, tetrahydrofuran, methyl tert-butyl ether, methanol, ethanol, isopropanol, trifluoroethanol, hexafluoroisopropanol, butanol, acetonitrile, dichloromethane, 1,2-dichloroethane, 1,4-dioxane, acetic acid, ethyl acetate, butyl acetate, amyl acetate, dimethyl sulfoxide, etc. N , N -Dimethylformamide, N One or more of methylpyrrolidone and methyl ethyl ketone, wherein the reaction temperature is 10–280 °C.

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