Phthalonitrile-terminated polyphenyl ether and preparation method and application thereof

[0041] Example 1

[0042] The synthesis route of the phthalonitrile-terminated polyphenylene ether prepared in this example is as follows:

[0043]

[0044] The preparation process of above-mentioned phthalonitrile-terminated polyphenylene ether comprises the following steps:

[0045] (1) Obtain a double-terminated hydroxyl polyphenylene ether solution under the action of a catalyst through oxidative copolymerization of phenolic monomers;

[0046] (11) Add 37.25g of 2,6-xylenol, 34.80g of bisphenol A and an organic solvent composed of 143.30g of toluene and 14.90g of methanol in sequence in the reaction kettle, and stir until the phenolic monomers are completely dissolved; then add 0.6g branched polyethyleneimine (Mn=600) and 0.80g cuprous bromide hydrobromic acid solution A (prepared with 0.10g cuprous oxide and 2.50g 48% hydrobromic acid in advance), after mixing uniformly 150sccm of oxygen was introduced, and the reaction was carried out at 20°C for 3 hours;

[0047] (12) After the reaction was completed, 5ml of 10% trisodium nitrilotriacetate aqueous solution was added to the reaction kettle, stirred and reacted at 70°C for 1 hour, and then the water phase was removed by liquid-liquid centrifugation to obtain 72g of double-terminated hydroxyl polyphenylene ether oligomer solution;

[0048] (2) Add 7.2 g of sodium hydroxide solution with a concentration of 2 mol/L to the double-terminated hydroxyl polyphenylene ether oligomer solution obtained in step (1), stir and react at 40°C for 120 minutes, and then remove the aqueous phase by liquid-liquid centrifugation to obtain Purified double-terminated hydroxyl polyphenylene ether oligomer solution;

[0049] (3) add 4.50g 4-nitrophthalonitrile and 39.00g anhydrous potassium carbonate (potassium carbonate and the Hydroxyl molar ratio is 2.3:1), stirred and reacted at 50°C for 24h, after the reaction, distilled and concentrated the obtained solution to 100mL, then added 2500mL of methanol to precipitate out, filtered and washed 3 times with methanol, and then dried in vacuum at 100°C After 12 hours, the phthalonitrile-terminated polyphenylene ether shown in formula (1) was obtained.

[0050]

[0051] The phthalonitrile-terminated polyphenylene ether prepared in this example is subjected to infrared testing, and the obtained infrared spectrum is as follows: figure 1 shown. It can be seen from the figure, 1306cm-1, 1227cm -1 , 1020cm -1 It is the vibration characteristic absorption peak of benzene ring C-O; 1602cm -1 and 1504cm -1 It is the characteristic absorption peak of stretching vibration of benzene ring skeleton C=C; 2956cm -1 , 2860cm -1 It is the characteristic absorption peak of the stretching vibration of methyl C-H on the benzene ring; 1379cm -1 It is the characteristic absorption peak of methyl C-H bending vibration on the benzene ring, 857cm -1 It is the characteristic absorption peak of C-H bending vibration on the benzene ring. The infrared spectrogram obtained by the infrared test of the phthalonitrile-terminated polyphenylene ether is basically consistent with the standard infrared spectrogram of traditional polyphenylene ether, indicating that the method of the present invention can effectively prepare polyphenylene ether products. At the same time, there are some differences in the spectrum, 2230cm -1 It is the characteristic absorption peak of the stretching vibration of the cyano group C=N. This indicated that the end-capping reaction between 4-nitrophthalonitrile and double-terminated hydroxyl polyphenylene ether occurred successfully.

[0052] Example 2

[0053] The synthesis route of the phthalonitrile-terminated polyphenylene ether prepared in this example is as follows:

[0054]

[0055] The preparation process of above-mentioned phthalonitrile-terminated polyphenylene ether comprises the following steps:

[0056] (1) Obtain a double-terminated hydroxyl polyphenylene ether solution under the action of a catalyst through oxidative copolymerization of phenolic monomers;

[0057] (11) Add 382.75g of 2,6-dimethylphenol, 29.70g of tetramethylbisphenol A and an organic solvent composed of 633.2g of toluene and 65.2g of methanol in sequence in the reaction kettle, and stir until the phenolic monomers are completely Dissolve, add 4.80g N,N-dimethylbutylamine, 1.60g branched polyethyleneimine (Mn=600) and 2.80g cuprous bromide hydrobromic acid solution (pre-prepared with 0.30g cuprous oxide and 2.50 g 48% hydrobromic acid), mix well and feed oxygen at 150 sccm, react at 60°C for 1 hour;

[0058] (12) After the reaction, add 40ml of 10% tetrasodium ethylenediaminetetraacetic acid aqueous solution into the reaction kettle, stir and react at 70°C for 1 hour, and then remove the water phase by liquid-liquid centrifugation to obtain 411g of double-terminated hydroxyl polyphenylene ether oligomer solution ;

[0059] (2) Add 13.7 g of sodium hydroxide solution with a concentration of 10 mol/L to the double-terminated hydroxyl polyphenylene ether oligomer solution obtained in step (1), stir and react at 70°C for 30 minutes, and then remove the aqueous phase by liquid-liquid centrifugation to obtain Purified double-terminated hydroxyl polyphenylene ether oligomer solution;

[0060] (3) Add 4.50g 4-nitrophthalonitrile and 35.00g anhydrous potassium carbonate (anhydrous potassium carbonate and oil phase The molar ratio of the hydroxyl group is 2.3:1), stirred and reacted at 120°C for 10h, after the reaction, the resulting solution was distilled and concentrated to 400mL, then added to 2500mL methanol to precipitate, filtered and washed with methanol for 3 times, and then heated at 100°C Vacuum-dried for 12 hours to obtain phthalonitrile-terminated polyphenylene ether as shown in formula (2).

[0061]

[0062] Example 3

[0063] The synthesis route of the phthalonitrile-terminated polyphenylene ether prepared in this example is as follows:

[0064]

[0065] The preparation process of above-mentioned phthalonitrile-terminated polyphenylene ether comprises the following steps:

[0066] (1) Obtain a double-terminated hydroxyl polyphenylene ether solution under the action of a catalyst through oxidative copolymerization of phenolic monomers;

[0067] (11) Add 133.50g of 2,6-dimethylphenol, 24.50g of bisphenol F and an organic solvent composed of 430g of toluene and 43.2g of methanol to the reaction kettle in sequence, and stir until the phenolic monomers are completely dissolved; then add 4.50g N,N-dimethylbutylamine, 1.50g branched polyethyleneimine (Mn=600) and 2.80g cuprous bromide hydrobromic acid solution (pre-prepared with 0.30g cuprous oxide and 2.50g 48% Hydrobromic acid preparation), after mixing evenly, feed oxygen at 150 sccm, and react at 40°C for 2 hours;

[0068] (12) After the reaction, add 20ml of 10% tetrasodium ethylenediaminetetraacetic acid aqueous solution to the reaction kettle, stir and react at 70°C for 1 hour, and then remove the water phase by liquid-liquid centrifugation to obtain 577.00g of double-terminated hydroxyl polyphenylene ether oligomer solution;

[0069](2) Add 38 g of sodium hydroxide solution with a concentration of 3 mol/L to the double-terminated hydroxyl polyphenylene ether oligomer solution obtained in step (1), stir and react at 50°C for 70 minutes, and then remove the aqueous phase by liquid-liquid centrifugation to obtain purified After the double-terminated hydroxyl polyphenylene ether oligomer solution;

[0070] (3) Add 4.3g 4-nitrophthalonitrile and 33.00g anhydrous potassium carbonate (anhydrous potassium carbonate and oil phase The molar ratio of the hydroxyl group is 1.8:1), stirred and reacted at 60°C for 15h, after the reaction, the obtained solution was distilled and concentrated to 400mL, then added to 2500mL of methanol to precipitate, filtered and washed with methanol for 3 times, and then heated at 100°C Vacuum-dried for 12 hours to obtain phthalonitrile-terminated polyphenylene ether as shown in formula (3).

[0071]