Bifunctional hydroxyl-terminated polyphenylene ether and its preparation method and application

Abstract

The application discloses a kind of bifunctionality end hydroxyl polyphenyl ether and its preparation method and application, the preparation method of bifunctionality end hydroxyl polyphenyl ether, comprising the following steps: monohydric phenol, dihydric phenol, copper catalyst solution, amine compound and solvent are mixed, and first oxygenation reaction is carried out;Subsequently, chelating agent solution is added to carry out chelation reaction, then second oxygenation reaction is carried out again;After reaction, copper catalyst is removed, and the bifunctionality end hydroxyl polyphenyl ether solution is prepared.Except the solvent and amine compound in the bifunctionality end hydroxyl polyphenyl ether solution, and the bifunctionality end hydroxyl polyphenyl ether is prepared.The oxygenation reaction is carried out after chelation reaction in the application, and the functionality of end hydroxyl polyphenyl ether is further improved to 1.97-1.99, and PDI is less than 1.8, and its inherent viscosity and PDI do not obviously increase.

Description

Technical Field

[0001] This invention belongs to the field of polymer synthesis technology, specifically relating to a bifunctional hydroxyl-terminated polyphenylene ether, its preparation method, and its application. Background Technology

[0002] Bifunctional polyphenylene ether resins are polyphenylene ether resins with active functional groups at both ends of their molecular chains. They mainly include bifunctional hydroxyl-terminated polyphenylene ethers and bifunctional alkenyl-terminated polyphenylene ethers. Their terminal hydroxyl or alkenyl groups possess high reactivity and can undergo cross-linking reactions with thermosetting resins such as epoxy resins, cyanate ester resins, and hydrocarbon resins to form stable three-dimensional network structures. Based on the inherent low dielectric loss, low moisture absorption, and high heat resistance of polyphenylene ethers, this type of resin has become one of the key materials for preparing high-frequency, high-speed copper-clad laminates. Its functionality directly determines the cross-linking density of the cured product, thus affecting the physicochemical properties of the final product, such as thermomechanical properties, moisture resistance, and dielectric properties.

[0003] Existing methods for preparing difunctional hydroxyl-terminated polyphenylene ethers often lead to a significant increase in the polydispersity index (PDI) when increasing functionality, resulting in limitations on functionality (difficulty in approaching the theoretical value of 2.0) and difficulties in controlling molecular weight distribution. Furthermore, the performance of difunctional alkenyl polyphenylene ethers is strongly dependent on the functionality and molecular weight distribution characteristics of the precursor difunctional hydroxyl-terminated polyphenylene ether.

[0004] Therefore, developing a method for preparing a bifunctional hydroxyl-terminated polyphenylene ether with a functionality closer to 2.0 and a lower PDI is of great significance. Summary of the Invention

[0005] To address the problems mentioned in the background section, the present invention aims to provide a bifunctional hydroxyl-terminated polyphenylene ether, its preparation method, and its applications. The bifunctional hydroxyl-terminated polyphenylene ether of the present invention, and the bifunctional alkenyl polyphenylene ether prepared therefrom, both possess high functionality (closer to the theoretical value of 2.0) and low PDI, simultaneously meeting the requirements of high-frequency, high-speed copper clad laminates for the functionality and molecular weight distribution of resin raw materials.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows: On one hand, the present invention provides a method for preparing a bifunctional hydroxyl-terminated polyphenylene ether, comprising the following steps:

[0007] A monohydric phenol, a dihydric phenol, a copper catalyst solution, an amine compound, and a solvent were mixed and subjected to a first oxygenation reaction. Subsequently, a chelating agent solution was added to carry out a chelation reaction, followed by a second oxygenation reaction. After the reaction was completed, the copper catalyst was removed to obtain a bifunctional hydroxyl-terminated polyphenylene ether solution.

[0008] Furthermore, the process of removing the copper catalyst includes: performing liquid-liquid separation on the product after the second oxygenation reaction to remove the heavy phase copper catalyst solution and obtain the bifunctional terminal hydroxyl polyphenylene ether solution.

[0009] Furthermore, the liquid-liquid separation includes static phase separation or centrifugal separation.

[0010] Furthermore, the method includes the following steps: removing the solvent and amine compounds from the difunctional hydroxyl-terminated polyphenylene ether solution to obtain the difunctional hydroxyl-terminated polyphenylene ether.

[0011] Furthermore, the solvent and amine compounds in the bifunctional terminal hydroxyl polyphenylene ether solution are removed by vacuum drying or high-temperature devolatilization extrusion.

[0012] Furthermore, the monohydric phenol includes 2,6-dimethylphenol;

[0013] And / or, the diphenol includes at least one of tetramethylbisphenol A and tetramethylbiphenyl;

[0014] And / or, the copper catalyst solution includes at least one of copper bromide solution and cuprous bromide solution; preferably, the copper catalyst solution is cuprous bromide solution, which is prepared by cuprous oxide and hydrobromic acid;

[0015] And / or, the solvent includes toluene;

[0016] And / or, the chelating agent solution is an aqueous solution of sodium nitrilotriacetate or sodium ethylenediaminetetraacetate; preferably, the aqueous solution of sodium nitrilotriacetate is an aqueous solution of trisodium nitrilotriacetate; preferably, the aqueous solution of sodium ethylenediaminetetraacetate is an aqueous solution of tetrasodium ethylenediaminetetraacetate.

[0017] Furthermore, the molar ratio of the monohydric phenol to the dihydric phenol is (2-30):1, preferably (2-15):1.

[0018] Furthermore, the molar ratio of the chelating agent in the chelating agent solution to the copper ions in the copper catalyst solution is (2-6):1.

[0019] Furthermore, the amine compound is selected from monotertiary amines, or at least one of monotertiary amines, monoprimary amines, monosecondary amines, and diamines;

[0020] Preferably, the monotertiary amine includes at least one of N,N-dimethyl-n-butylamine and N,N-dimethylcyclohexylamine;

[0021] Preferably, the primary amine includes at least one of n-butylamine, sec-butylamine, tert-butylamine, n-pentylamine, n-hexylamine, and cyclohexylamine;

[0022] Preferably, the monohydric secondary amine includes at least one of di-n-butylamine, di-tert-butylamine, and di-n-hexylamine;

[0023] Preferably, the diamine includes at least one selected from tetramethylethylenediamine, tetramethylpropylenediamine, and tetramethylbutylenediamine;

[0024] Preferably, the molar ratio of the monohydric tertiary amine to the monohydric phenol is (0.01-0.1):1, more preferably (0.03-0.08):1;

[0025] Preferably, the molar ratio of the monohydric primary amine to the monohydric phenol is (0-0.04):1, more preferably (0.01-0.03):1;

[0026] Preferably, the molar ratio of the monohydric secondary amine to the monohydric phenol is (0-0.04):1, more preferably (0.01-0.03):1;

[0027] Preferably, the molar ratio of the diamine to the monohydric phenol is (0-0.01):1, more preferably (0.001-0.005):1.

[0028] Furthermore, in the first oxygenation reaction, the molar ratio of the total amount of oxygen introduced to the monohydric phenol is (0.5-1.2):1, preferably (0.7-1.0):1;

[0029] In the first oxygenation reaction, the reaction temperature is 15-65℃, preferably 20-60℃;

[0030] In the first oxygenation reaction, the reaction time is 1-5 hours, preferably 2-4 hours.

[0031] Furthermore, the reaction temperature of the chelation reaction is 50-90℃, preferably 60-80℃;

[0032] The chelation reaction takes 30-90 minutes, preferably 45-75 minutes.

[0033] Furthermore, in the second oxygenation reaction, the molar ratio of the total amount of oxygen introduced to the monohydric phenol is (0.08-0.8):1, preferably (0.2-0.6):1;

[0034] In the second oxygenation reaction, the reaction temperature is 20-80℃, preferably 30-70℃;

[0035] In the second oxygenation reaction, the reaction time is 0.2-8 hours, preferably 1-4 hours.

[0036] On the other hand, the present invention provides a bifunctional hydroxyl-terminated polyphenylene ether, which is prepared by any of the preparation methods described above.

[0037] Further, the functionality of the bifunctional hydroxyl-terminated polyphenylene ether is 1.95-1.99, and the polydispersity index (PDI) is less than 1.85; preferably, the functionality of the bifunctional hydroxyl-terminated polyphenylene ether is 1.97-1.99, and the polydispersity index (PDI) is less than 1.80.

[0038] On the other hand, the present invention provides a bifunctional terminal alkenyl polyphenylene ether, which is prepared by esterification reaction of the above-mentioned bifunctional terminal hydroxyl polyphenylene ether with an acylation reagent.

[0039] Further, the preparation method of the difunctional end-alkenyl polyphenylene ether specifically includes: mixing a monohydric phenol, a dihydric phenol, a copper catalyst solution, an amine compound, and a solvent, and carrying out a first oxygenation reaction; subsequently adding a chelating agent solution to carry out a chelation reaction, and then carrying out a second oxygenation reaction; after the reaction is completed, removing the copper catalyst to obtain a difunctional end-hydroxyl polyphenylene ether solution; adding an acylation reagent and an esterification catalyst to the difunctional end-hydroxyl polyphenylene ether solution to carry out an esterification reaction, and separating and purifying to obtain the difunctional end-alkenyl polyphenylene ether.

[0040] Furthermore, the acylation reagent includes at least one of acrylic anhydride and methacrylic anhydride, preferably methacrylic anhydride.

[0041] Furthermore, the reaction temperature of the esterification reaction is 80-120℃, preferably 90-110℃;

[0042] The esterification reaction takes 1-5 hours, preferably 2-4 hours.

[0043] Furthermore, the molar ratio of the acylation reagent to the diphenol is (2-4):1.

[0044] Furthermore, the esterification catalyst is 4-dimethylaminopyridine.

[0045] Furthermore, the separation and purification steps for obtaining the difunctional terminal alkenyl polyphenylene ether include: adding the product obtained from the reaction to a solvent to precipitate, separating, washing, and drying.

[0046] Further, the solvent is a poor solvent for polyphenylene ether; preferably, the poor solvent for polyphenylene ether includes C1-C4 alkyl alcohols; more preferably, the poor solvent for polyphenylene ether is methanol.

[0047] Furthermore, the separation and purification process may include a concentration process.

[0048] Further, the functionality of the difunctional terminal alkenyl polyphenylene ether is 1.95-1.99, and the polydispersity index (PDI) is less than 1.8; preferably, the functionality of the difunctional terminal alkenyl polyphenylene ether is 1.97-1.99, and the polydispersity index (PDI) is less than 1.75.

[0049] In another aspect, the present invention provides the application of the above-described difunctional hydroxyl-terminated polyphenylene ether and any of the above-described difunctional alkenyl polyphenylene ether in the preparation of high-frequency and high-speed copper-clad laminates.

[0050] In another aspect, the present invention provides a high-frequency, high-speed copper-clad laminate, comprising the aforementioned bifunctional hydroxyl-terminated polyphenylene ether and any of the aforementioned bifunctional alkenyl polyphenylene ethers.

[0051] Compared with the prior art, the present invention has the following beneficial effects:

[0052] This invention further increases the functionality of terminal hydroxyl polyphenylene ethers to 1.97-1.99 and achieves a PDI of less than 1.8 by subjecting an oxygenation reaction after chelation. The intrinsic viscosity and PDI do not show a significant increase. Esterification of the obtained difunctional terminal hydroxyl polyphenylene ether with an acylation reagent yields terminal alkenyl polyphenylene ethers with a functionality of 1.97-1.99 and a PDI of less than 1.75. Using the difunctional terminal hydroxyl polyphenylene ethers and difunctional terminal alkenyl polyphenylene ethers of this invention to prepare high-frequency, high-speed copper-clad laminates results in products with superior heat resistance, low moisture absorption, and dielectric stability. Attached Figure Description

[0053] Figure 1 This is a partial 1H NMR spectrum of the bifunctional hydroxyl-terminated polyphenylene ether prepared in Example 1 of the present invention;

[0054] Figure 2 This is a partial 1H NMR spectrum of the bifunctional terminal alkenyl polyphenylene ether prepared in Example 2 of the present invention. Detailed Implementation

[0055] To enable those skilled in the art to more clearly understand the technical solutions described in this invention, the following embodiments are provided for illustration. It should be noted that the following embodiments do not constitute a limitation on the scope of protection claimed by this invention.

[0056] Unless otherwise specified, the raw materials, reagents or devices used in the following examples are available from conventional commercial sources or can be obtained by existing known methods.

[0057] Example 1

[0058] Preparation of bifunctional hydroxyl-terminated polyphenylene ethers:

[0059] Add 200.0 g of 2,6-dimethylphenol (1.639 mol), 35.0 g of tetramethylbisphenol A (0.123 mol), and 500.0 g of toluene to a reaction vessel, stir to dissolve, then add 6.0 g of N,N-dimethyl-n-butylamine (0.059 mol), 2.5 g of di-n-butylamine, 0.5 g of tetramethylethylenediamine, and 2.60 g of cuprous bromide solution (prepared with 0.20 g of cuprous oxide and 2.40 g of hydrobromic acid), mix well, and purge with oxygen (0.45 mol / h). React at 40°C for 3 h; then add 30 g of... A 10wt% trisodium triamcinolone aqueous solution was stirred at 70℃ for 60 min, then cooled to 50℃, and oxygen (0.33 mol / h) was continuously introduced and reacted at 50℃ for 2 h. After the reaction was completed, the product was separated into liquid and liquid phases to remove the heavy phase, and a difunctional hydroxyl-terminated polyphenylene ether solution was obtained. The difunctional hydroxyl-terminated polyphenylene ether solution was vacuum dried at 100℃ for 8 h to obtain the difunctional hydroxyl-terminated polyphenylene ether.

[0060] Example 2

[0061] Preparation of bifunctional terminal alkenyl polyphenylene ethers:

[0062] 200.0 g of 2,6-dimethylphenol (1.639 mol), 35.0 g of tetramethylbisphenol A (0.123 mol), and 500.0 g of toluene were added to a reaction vessel and stirred until dissolved. Then, 6.0 g of N,N-dimethyl-n-butylamine (0.059 mol), 2.5 g of di-n-butylamine, 0.5 g of tetramethylethylenediamine, and 2.60 g of cuprous bromide solution (prepared with 0.20 g of cuprous oxide and 2.40 g of hydrobromic acid) were added and mixed thoroughly. Oxygen (0.45 mol / h) was introduced, and the reaction was carried out at 40 °C for 3 h. Subsequently, 30 g of 10 wt% trisodium triamcinolone acetonide aqueous solution was added, and the reaction was stirred at 70 °C for 60 min. The temperature was then lowered to 50 °C, and oxygen (0.33 mol / h) was introduced and the reaction was carried out at 50 °C for 2 h. After the reaction was completed, the product was separated into liquid and liquid phases to remove the heavy phase, yielding a bifunctional hydroxyl-terminated polyphenylene ether solution.

[0063] 4.3 g of 4-dimethylaminopyridine and 52.0 g of methacrylic anhydride were added to a solution of difunctional hydroxyl-terminated polyphenylene ether, and the mixture was reacted at 100 °C for 3 h. After the reaction was completed, the resulting solution was concentrated by distillation to 570 g, and then added to 3000 g of methanol. The precipitate was precipitated, filtered, washed three times with methanol, and dried under vacuum at 100 °C for 8 h to obtain difunctional alkenyl polyphenylene ether.

[0064] Example 3

[0065] Preparation of bifunctional hydroxyl-terminated polyphenylene ethers:

[0066] Add 180.0 g of 2,6-dimethylphenol (1.475 mol), 40.8 g of tetramethylbisphenol A (0.144 mol), and 500.0 g of toluene to a reaction vessel, stir to dissolve, then add 9.0 g of N,N-dimethylcyclohexylamine (0.071 mol), 2.0 g of n-butylamine, 0.6 g of tetramethylethylenediamine, and 2.60 g of cuprous bromide solution (prepared with 0.20 g of cuprous oxide and 2.40 g of hydrobromic acid), mix well, and purge with oxygen (0.48 mol / h). React at 45°C for 2.5 h; then add 30 g of... A 10wt% trisodium triamcinolone aqueous solution was stirred at 70℃ for 60 min, then cooled to 50℃, and oxygen (0.12 mol / h) was continuously introduced and reacted at 50℃ for 3 h. After the reaction was completed, the product was separated into liquid and liquid phases to remove the heavy phase, and a difunctional hydroxyl-terminated polyphenylene ether solution was obtained. The difunctional hydroxyl-terminated polyphenylene ether solution was vacuum dried at 100℃ for 8 h to obtain the difunctional hydroxyl-terminated polyphenylene ether.

[0067] Example 4

[0068] Preparation of bifunctional terminal alkenyl polyphenylene ethers:

[0069] 180.0 g of 2,6-dimethylphenol (1.475 mol), 40.8 g of tetramethylbisphenol A (0.144 mol), and 500.0 g of toluene were added to a reaction vessel and stirred until dissolved. Then, 9.0 g of N,N-dimethylcyclohexylamine (0.071 mol), 2.0 g of n-butylamine, 0.6 g of tetramethylethylenediamine, and 2.60 g of cuprous bromide solution (prepared with 0.20 g of cuprous oxide and 2.40 g of hydrobromic acid) were added and mixed thoroughly. Oxygen (0.48 mol / h) was introduced, and the reaction was carried out at 45 °C for 2.5 h. Subsequently, 30 g of 10 wt% trisodium triamcinolone acetonide aqueous solution was added, and the reaction was stirred at 70 °C for 60 min. The temperature was then lowered to 50 °C, and oxygen (0.12 mol / h) was introduced and the reaction was carried out at 50 °C for 3 h. After the reaction was completed, the product was separated into liquid and liquid phases to remove the heavy phase, yielding a bifunctional hydroxyl-terminated polyphenylene ether solution.

[0070] 4.3 g of 4-dimethylaminopyridine and 58.0 g of methacrylic anhydride were added to a solution of difunctional hydroxyl-terminated polyphenylene ether, and the mixture was reacted at 100 °C for 4 h. After the reaction was completed, the resulting solution was concentrated by distillation to 570 g, and then added to 3000 g of methanol. The precipitate was formed, filtered, washed three times with methanol, and dried under vacuum at 100 °C for 8 h to obtain difunctional alkenyl polyphenylene ether.

[0071] Example 5

[0072] Preparation of bifunctional hydroxyl-terminated polyphenylene ethers:

[0073] Add 200.0 g of 2,6-dimethylphenol (1.639 mol), 32.0 g of tetramethylbisphenol A (0.113 mol), and 500.0 g of toluene to a reaction vessel, stir to dissolve, then add 8.0 g of N,N-dimethyl-n-butylamine (0.079 mol), 1.5 g of n-butylamine, 0.6 g of tetramethylpropanediamine, and 2.60 g of cuprous bromide solution (prepared with 0.20 g of cuprous oxide and 2.40 g of hydrobromic acid), mix well, and purge with oxygen (0.39 mol / h). React at 35°C for 4 h; then add 30 g of... A 10wt% trisodium triamcinolone aqueous solution was stirred at 70℃ for 60 min, then cooled to 40℃, and oxygen (0.17 mol / h) was continuously introduced and reacted at 40℃ for 4 h. After the reaction was completed, the product was separated into liquid and liquid phases to remove the heavy phase, and a difunctional hydroxyl-terminated polyphenylene ether solution was obtained. The difunctional hydroxyl-terminated polyphenylene ether solution was vacuum dried at 100℃ for 8 h to obtain the difunctional hydroxyl-terminated polyphenylene ether.

[0074] Example 6

[0075] Preparation of bifunctional terminal alkenyl polyphenylene ethers:

[0076] 200.0 g of 2,6-dimethylphenol (1.639 mol), 32.0 g of tetramethylbisphenol A (0.113 mol), and 500.0 g of toluene were added to a reaction vessel and stirred until dissolved. Then, 8.0 g of N,N-dimethyl-n-butylamine (0.079 mol), 1.5 g of n-butylamine, 0.6 g of tetramethylpropanediamine, and 2.60 g of cuprous bromide solution (prepared with 0.20 g of cuprous oxide and 2.40 g of hydrobromic acid) were added and mixed thoroughly. Oxygen was introduced (0.39 mol / h), and the reaction was carried out at 35 °C for 4 h. Subsequently, 30 g of 10 wt% trisodium triamcinolone acetonide aqueous solution was added, and the reaction was stirred at 70 °C for 60 min. The temperature was then lowered to 40 °C, and oxygen was introduced (0.17 mol / h), and the reaction was carried out at 40 °C for 4 h. After the reaction was completed, the product was separated into liquid and liquid phases to remove the heavy phase, yielding a bifunctional hydroxyl-terminated polyphenylene ether solution.

[0077] 4.3 g of 4-dimethylaminopyridine and 52.0 g of methacrylic anhydride were added to a solution of difunctional hydroxyl-terminated polyphenylene ether, and the mixture was reacted at 100 °C for 2.5 h. After the reaction was completed, the resulting solution was concentrated by distillation to 570 g, and then added to 3000 g of methanol. The precipitate was precipitated, filtered, washed three times with methanol, and dried under vacuum at 100 °C for 8 h to obtain difunctional alkenyl polyphenylene ether.

[0078] Example 7

[0079] Preparation of bifunctional hydroxyl-terminated polyphenylene ethers:

[0080] Add 200.0 g of 2,6-dimethylphenol (1.639 mol), 40.8 g of tetramethylbisphenol A (0.144 mol), and 500.0 g of toluene to a reaction vessel, stir to dissolve, then add 10.0 g of N,N-dimethylcyclohexylamine (0.079 mol), 3.0 g of di-n-butylamine, 0.8 g of tetramethylethylenediamine, and 3.12 g of cuprous bromide solution (prepared with 0.24 g of cuprous oxide and 2.88 g of hydrobromic acid), mix well, and purge with oxygen (0.78 mol / h). React at 45°C for 2 h; then add 30 g of... A 10wt% trisodium triamcinolone aqueous solution was stirred at 70℃ for 60 min, then cooled to 50℃, and oxygen (0.24 mol / h) was continuously introduced and reacted at 50℃ for 2.5 h. After the reaction was completed, the product was separated into liquid and liquid phases to remove the heavy phase, and a difunctional hydroxyl-terminated polyphenylene ether solution was obtained. The difunctional hydroxyl-terminated polyphenylene ether solution was vacuum dried at 100℃ for 8 h to obtain the difunctional hydroxyl-terminated polyphenylene ether.

[0081] Example 8

[0082] Preparation of bifunctional terminal alkenyl polyphenylene ethers:

[0083] 200.0 g of 2,6-dimethylphenol (1.639 mol), 40.8 g of tetramethylbisphenol A (0.144 mol), and 500.0 g of toluene were added to a reaction vessel and stirred until dissolved. Then, 10.0 g of N,N-dimethylcyclohexylamine (0.079 mol), 3.0 g of di-n-butylamine, 0.8 g of tetramethylethylenediamine, and 3.12 g of cuprous bromide solution (prepared with 0.24 g of cuprous oxide and 2.88 g of hydrobromic acid) were added and mixed thoroughly. Oxygen (0.78 mol / h) was introduced, and the reaction was carried out at 45 °C for 2 h. Subsequently, 30 g of 10 wt% trisodium triamcinolone acetonide aqueous solution was added, and the reaction was stirred at 70 °C for 60 min. The temperature was then lowered to 50 °C, and oxygen (0.24 mol / h) was introduced again, and the reaction was carried out at 50 °C for 2.5 h. After the reaction was completed, the product was separated into liquid and liquid phases to remove the heavy phase, yielding a bifunctional hydroxyl-terminated polyphenylene ether solution.

[0084] 4.3 g of 4-dimethylaminopyridine and 58.0 g of methacrylic anhydride were added to a solution of difunctional hydroxyl-terminated polyphenylene ether, and the mixture was reacted at 100 °C for 4 h. After the reaction was completed, the resulting solution was concentrated by distillation to 570 g, and then added to 3000 g of methanol. The precipitate was formed, filtered, washed three times with methanol, and dried under vacuum at 100 °C for 8 h to obtain difunctional alkenyl polyphenylene ether.

[0085] Comparative Example 1

[0086] Preparation of bifunctional hydroxyl-terminated polyphenylene ethers:

[0087] 200.0 g of 2,6-dimethylphenol (1.639 mol), 35.0 g of tetramethylbisphenol A (0.123 mol), and 500.0 g of toluene were added to a reaction vessel and stirred until dissolved. Then, 6.0 g of N,N-dimethyl-n-butylamine (0.059 mol), 2.5 g of di-n-butylamine, 0.5 g of tetramethylethylenediamine, and 2.60 g of cuprous bromide solution (prepared with 0.20 g of cuprous oxide and 2.40 g of hydrobromic acid) were added and mixed thoroughly. Oxygen (0.45 mol / h) was introduced and the reaction was carried out at 40 °C for 3 h. Subsequently, 30 g of 10 wt% trisodium triamcinolone acetonide aqueous solution was added and the reaction was stirred at 70 °C for 60 min. After the reaction was completed, the product was separated into liquid and liquid phases to remove the heavy phase, and a difunctional hydroxyl-terminated polyphenylene ether solution was obtained. The difunctional hydroxyl-terminated polyphenylene ether solution was vacuum dried at 100 °C for 8 h to obtain the difunctional hydroxyl-terminated polyphenylene ether.

[0088] Comparative Example 2

[0089] Preparation of bifunctional terminal alkenyl polyphenylene ethers:

[0090] 200.0 g of 2,6-dimethylphenol (1.639 mol), 35.0 g of tetramethylbisphenol A (0.123 mol), and 500.0 g of toluene were added to a reaction vessel and stirred until dissolved. Then, 6.0 g of N,N-dimethyl-n-butylamine (0.059 mol), 2.5 g of di-n-butylamine, 0.5 g of tetramethylethylenediamine, and 2.60 g of cuprous bromide solution (prepared with 0.20 g of cuprous oxide and 2.40 g of hydrobromic acid) were added and mixed thoroughly. Oxygen (0.45 mol / h) was introduced and the reaction was carried out at 40 °C for 3 h. Subsequently, 30 g of 10 wt% trisodium triamcinolone acetonide aqueous solution was added and the reaction was stirred at 70 °C for 60 min. After the reaction was completed, the product was separated into liquid and liquid phases to remove the heavy phase, yielding a bifunctional hydroxyl-terminated polyphenylene ether solution.

[0091] 4.3 g of 4-dimethylaminopyridine and 52.0 g of methacrylic anhydride were added to a solution of difunctional hydroxyl-terminated polyphenylene ether, and the mixture was reacted at 100 °C for 3 h. After the reaction was completed, the resulting solution was concentrated by distillation to 570 g, and then added to 3000 g of methanol. The precipitate was precipitated, filtered, washed three times with methanol, and dried under vacuum at 100 °C for 8 h to obtain difunctional alkenyl polyphenylene ether.

[0092] Comparative Example 3

[0093] Preparation of bifunctional hydroxyl-terminated polyphenylene ethers:

[0094] Add 200.0 g of 2,6-dimethylphenol (1.639 mol), 35.0 g of tetramethylbisphenol A (0.123 mol), and 500.0 g of toluene to a reaction vessel, stir to dissolve, then add 6.0 g of N,N-dimethyl-n-butylamine (0.059 mol), 2.5 g of di-n-butylamine, 0.5 g of tetramethylethylenediamine, and 2.60 g of cuprous bromide solution (prepared with 0.20 g of cuprous oxide and 2.40 g of hydrobromic acid), mix well, and purge with oxygen (0.45 mol / h). React at 40°C for 3 h; then raise the temperature to 50°C and continue purging with oxygen (0.33 mol / h) for 1 h; after the reaction is complete, add 30 g of... A 10wt% trisodium triamcinolone aqueous solution was stirred at 70℃ for 60 min. After the reaction was completed, the aqueous phase was removed by standing to obtain a difunctional hydroxyl-terminated polyphenylene ether solution. The difunctional hydroxyl-terminated polyphenylene ether solution was vacuum dried at 100℃ for 8 h to obtain the difunctional hydroxyl-terminated polyphenylene ether.

[0095] Comparative Example 4

[0096] Preparation of bifunctional terminal alkenyl polyphenylene ethers:

[0097] 200.0 g of 2,6-dimethylphenol (1.639 mol), 35.0 g of tetramethylbisphenol A (0.123 mol), and 500.0 g of toluene were added to a reaction vessel and stirred until dissolved. Then, 6.0 g of N,N-dimethyl-n-butylamine (0.059 mol), 2.5 g of di-n-butylamine, 0.5 g of tetramethylethylenediamine, and 2.60 g of cuprous bromide solution (prepared with 0.20 g of cuprous oxide and 2.40 g of hydrobromic acid) were added and mixed thoroughly. Oxygen (0.45 mol / h) was introduced and the reaction was carried out at 40 °C for 3 h. Subsequently, the temperature was raised to 50 °C and oxygen (0.33 mol / h) was introduced and the reaction was carried out for 1 h. After the reaction was completed, 30 g of 10 wt% trisodium triamcinolone aqueous solution was added and the reaction was stirred at 70 °C for 60 min. After the reaction was completed, the aqueous phase was removed by standing to obtain a bifunctional hydroxyl-terminated polyphenylene ether solution.

[0098] 4.3 g of 4-dimethylaminopyridine and 52.0 g of methacrylic anhydride were added to a solution of difunctional hydroxyl-terminated polyphenylene ether, and the mixture was reacted at 100 °C for 3 h. After the reaction was completed, the resulting solution was concentrated by distillation to 570 g, and then added to 3000 g of methanol. The precipitate was precipitated, filtered, washed three times with methanol, and dried under vacuum at 100 °C for 8 h to obtain difunctional alkenyl polyphenylene ether.

[0099] Comparative Example 5

[0100] Preparation of bifunctional hydroxyl-terminated polyphenylene ethers:

[0101] Add 200.0 g of 2,6-dimethylphenol (1.639 mol), 35.0 g of tetramethylbisphenol A (0.123 mol), and 500.0 g of toluene to a reaction vessel, stir to dissolve, then add 6.0 g of N,N-dimethyl-n-butylamine (0.059 mol), 2.5 g of di-n-butylamine, 0.5 g of tetramethylethylenediamine, and 2.60 g of cuprous bromide solution (prepared with 0.20 g of cuprous oxide and 2.40 g of hydrobromic acid), mix well, and purge with oxygen (0.45 mol / h). React at 40°C for 3 h; then raise the temperature to 50°C and continue purging with oxygen (0.33 mol / h) for 2 h; after the reaction is complete, add 30 g of... A 10wt% trisodium triamcinolone aqueous solution was stirred at 70℃ for 60 min. After the reaction was completed, the aqueous phase was removed by standing to obtain a difunctional hydroxyl-terminated polyphenylene ether solution. The difunctional hydroxyl-terminated polyphenylene ether solution was vacuum dried at 100℃ for 8 h to obtain the difunctional hydroxyl-terminated polyphenylene ether.

[0102] Comparative Example 6

[0103] Preparation of bifunctional terminal alkenyl polyphenylene ethers:

[0104] 200.0 g of 2,6-dimethylphenol (1.639 mol), 35.0 g of tetramethylbisphenol A (0.123 mol), and 500.0 g of toluene were added to a reaction vessel and stirred until dissolved. Then, 6.0 g of N,N-dimethyl-n-butylamine (0.059 mol), 2.5 g of di-n-butylamine, 0.5 g of tetramethylethylenediamine, and 2.60 g of cuprous bromide solution (prepared with 0.20 g of cuprous oxide and 2.40 g of hydrobromic acid) were added and mixed thoroughly. Oxygen (0.45 mol / h) was introduced and the reaction was carried out at 40 °C for 3 h. Subsequently, the temperature was raised to 50 °C and oxygen (0.33 mol / h) was introduced and the reaction was carried out for 2 h. After the reaction was completed, 30 g of 10 wt% trisodium triamcinolone aqueous solution was added and the reaction was stirred at 70 °C for 60 min. After the reaction was completed, the aqueous phase was removed by standing to obtain a bifunctional hydroxyl-terminated polyphenylene ether solution.

[0105] 4.3 g of 4-dimethylaminopyridine and 52.0 g of methacrylic anhydride were added to a solution of difunctional hydroxyl-terminated polyphenylene ether, and the mixture was reacted at 100 °C for 3 h. After the reaction was completed, the resulting solution was concentrated by distillation to 570 g, and then added to 3000 g of methanol. The precipitate was precipitated, filtered, washed three times with methanol, and dried under vacuum at 100 °C for 8 h to obtain difunctional alkenyl polyphenylene ether.

[0106] Performance testing

[0107] The bifunctional hydroxyl-terminated polyphenylene ether and bifunctional alkenyl-terminated polyphenylene ether prepared in the examples and comparative examples were subjected to relevant performance tests.

[0108] 1) Sensory evaluation

[0109] Nuclear magnetic resonance (NMR) tests were performed on the difunctional hydroxyl-terminated polyphenylene ether and the difunctional alkenyl-terminated polyphenylene ether prepared in the examples and comparative examples, respectively. The partial 1H NMR spectra of the difunctional hydroxyl-terminated polyphenylene ether prepared in Example 1 and the difunctional alkenyl-terminated polyphenylene ether prepared in Example 2 are shown below. Figure 1 and Figure 2 As shown.

[0110] In the figure, peak 1 at 7.06 ppm is the proton peak on the benzene ring of 2,6-dimethylphenyl (peak area is represented by A), peak 2 at 6.37 ppm and peak 3 at 5.74 ppm are the proton peaks of the =CH2 group on the methylpropene group at the end of the molecular chain (peak areas are represented by B and C), and peak 4 at 4.3 ppm is the proton peak of the phenolic hydroxyl group (peak area is represented by D).

[0111] Functionality is calculated using the following formula:

[0112]

[0113]

[0114] 2) Intrinsic viscosity

[0115] Using chloroform as a solvent, the intrinsic viscosity of the bifunctional hydroxyl-terminated polyphenylene ether and bifunctional alkenyl polyphenylene ether prepared in the examples and comparative examples was tested at 30°C using an Ubbelohde viscometer.

[0116] 3) Molecular weight and its distribution

[0117] Using tetrahydrofuran (THF) as the mobile phase and polystyrene (PS) as the standard sample, the molecular weight and polydispersity index (PDI) of the bifunctional hydroxyl-terminated polyphenylene ether and bifunctional alkenyl polyphenylene ether prepared in the examples and comparative examples were tested using gel permeation chromatography (GPC).

[0118] The performance test results of the bifunctional hydroxyl-terminated polyphenylene ethers prepared in the examples and comparative examples are shown in Table 1.

[0119] Table 1. Performance test results of the bifunctional hydroxyl-terminated polyphenylene ethers prepared in the examples and comparative examples.

[0120]

[0121] The performance test results of the bifunctional terminal alkenyl polyphenylene ethers prepared in the examples and comparative examples are shown in Table 2.

[0122] Table 2 Performance test results of the bifunctional terminal alkenyl polyphenylene ethers prepared in the examples and comparative examples

[0123]

[0124] As can be seen from Table 1, by performing a second oxygenation reaction after the chelation reaction, the bifunctional hydroxyl-terminated polyphenylene ether obtained by the present invention can achieve a functionality of 1.97-1.99 and a PDI of less than 1.8.

[0125] Compared with Example 1, Comparative Example 1 did not undergo a second oxygenation reaction after the chelation reaction, and its functionality was only 1.93, which was significantly lower than that of Example 1. However, its intrinsic viscosity and PDI did not change significantly.

[0126] Compared with Example 1, Comparative Example 3 underwent a second oxygenation reaction before the chelation reaction, and the reaction time was reduced to 1 hour. Although its functionality could also reach 1.97, its PDI increased significantly, reaching 1.88.

[0127] Compared with Example 1, Comparative Example 5 underwent a second oxygenation reaction before the chelation reaction, and the reaction time remained unchanged at 2 hours. It can be seen that its functionality can also reach 1.99, but its PDI further increased to 1.92.

[0128] As can be seen from Table 2, the functionality of difunctional end-hydroxyl polyphenylene ether synthesized by esterification reaction with acylation reagent based on difunctional end-hydroxyl polyphenylene ether with a functionality of 1.97-1.99 can also reach 1.97-1.99, and the PDI is less than 1.75.

[0129] Compared to Comparative Example 2, the difunctional terminal alkenyl polyphenylene ether obtained in Example 2 also exhibited higher functionality, and its intrinsic viscosity and PDI did not increase significantly. While Comparative Examples 4 and 6 showed improved functionality, their PDI gradually increased with the progress of the oxygenation reaction.

[0130] In summary, this invention, by subjecting a second oxygenation reaction after the chelation reaction, can increase the functionality of terminal hydroxyl polyphenylene ether to 1.97-1.99, with a PDI less than 1.8, while its intrinsic viscosity and PDI do not show a significant increase. Further esterification of the obtained bifunctional terminal hydroxyl polyphenylene ether with an acylation reagent yields terminal alkenyl polyphenylene ether with a functionality of 1.97-1.99 and a PDI less than 1.75.

[0131] The above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A method for preparing a bifunctional hydroxyl-terminated polyphenylene ether, characterized in that, Includes the following steps: A monohydric phenol, a dihydric phenol, a copper catalyst solution, an amine compound, and a solvent were mixed and subjected to a first oxygen-purifying reaction. Subsequently, a chelating agent solution was added to carry out a chelation reaction, followed by a second oxygen-purifying reaction. After the reaction was completed, the copper catalyst was removed to obtain a bifunctional hydroxyl-terminated polyphenylene ether solution. In the first oxygenation reaction, the molar ratio of the total amount of oxygen introduced to the monohydric phenol is (0.5-1.2):1; in the first oxygenation reaction, the reaction temperature is 15-65℃; in the first oxygenation reaction, the reaction time is 1-5h. In the second oxygenation reaction, the molar ratio of the total amount of oxygen introduced to the monohydric phenol is (0.08-0.8):1; in the second oxygenation reaction, the reaction temperature is 20-80℃; in the second oxygenation reaction, the reaction time is 0.2-8h.

2. The preparation method according to claim 1, characterized in that, It also includes the following steps: The difunctional hydroxyl-terminated polyphenylene ether is prepared by removing the solvent and amine compounds from the solution.

3. The preparation method according to claim 1 or 2, characterized in that, The monohydric phenol includes 2,6-dimethylphenol; And / or, the diphenol includes at least one of tetramethylbisphenol A and tetramethylbiphenyl. And / or, the copper catalyst solution includes at least one of copper bromide solution and cuprous bromide solution; And / or, the solvent includes toluene; And / or, the chelating agent solution is an aqueous solution of sodium triacetate or sodium ethylenediaminetetraacetate.

4. The preparation method according to claim 3, characterized in that, The copper catalyst solution is a cuprous bromide solution, which is prepared from cuprous oxide and hydrobromic acid.

5. The preparation method according to claim 3, characterized in that, The aqueous solution of sodium triacetate is an aqueous solution of trisodium triacetate.

6. The preparation method according to claim 3, characterized in that, The aqueous solution of sodium ethylenediaminetetraacetate is an aqueous solution of sodium ethylenediaminetetraacetate.

7. The preparation method according to claim 1 or 2, characterized in that, The molar ratio of the monohydric phenol to the dihydric phenol is (2-30):

1.

8. The preparation method according to claim 1 or 2, characterized in that, The amine compound is selected from monotertiary amines, or at least one of monotertiary amines, monoprimary amines, monosecondary amines, and diamines.

9. The preparation method according to claim 8, characterized in that, The monotertiary amine includes at least one of N,N-dimethyl-n-butylamine and N,N-dimethylcyclohexylamine.

10. The preparation method according to claim 8, characterized in that, The primary amine includes at least one of n-butylamine, sec-butylamine, tert-butylamine, n-pentylamine, n-hexylamine, and cyclohexylamine.

11. The preparation method according to claim 8, characterized in that, The monomethyl secondary amine includes at least one of di-n-butylamine, di-tert-butylamine, and di-n-hexylamine.

12. The preparation method according to claim 8, characterized in that, The diamine includes at least one of tetramethylethylenediamine, tetramethylpropylenediamine, and tetramethylbutylenediamine.

13. The preparation method according to claim 8, characterized in that, The molar ratio of the monohydric tertiary amine to the monohydric phenol is (0.01-0.1):

1.

14. The preparation method according to claim 1 or 2, characterized in that, The chelation reaction temperature is 50-90℃; the chelation reaction time is 30-90 min.

15. A bifunctional hydroxyl-terminated polyphenylene ether, characterized in that, It is prepared by any of the preparation methods described in claims 1-14.

16. A bifunctional terminal alkenyl polyphenylene ether, characterized in that, It is prepared by esterification reaction of the bifunctional terminal hydroxyl polyphenylene ether as described in claim 15 with an acylation agent.

17. The bifunctional terminal alkenyl polyphenylene ether according to claim 16, characterized in that, The acylation reagent includes at least one of acrylic anhydride and methacrylic anhydride.

18. The bifunctional terminal alkenyl polyphenylene ether according to claim 16, characterized in that, The esterification reaction is carried out at a temperature of 80-120℃ and for a time of 1-5 hours.

19. The use of the bifunctional hydroxyl-terminated polyphenylene ether of claim 15 and the bifunctional alkenyl polyphenylene ether of any one of claims 16-18 in the preparation of high-frequency and high-speed copper-clad laminates.

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