A method for quenching residual halogenated alkanes in a nucleophilic polymerization reaction

Abstract

The application provides a method for quenching residual halogenated alkanes in a nucleophilic polymerization reaction, in which a binary acidic monomer and a dihalogenated monomer are subjected to nucleophilic polymerization under an inert atmosphere, then a halogenated alkane is added for capping, after the capping is completed, an organic acid salt is added into a reaction kettle, and stirring is performed for quenching reaction. The method provided by the application can eliminate the excessive halogenated alkanes to the maximum extent, thereby avoiding the pollution of the residual halogenated alkanes to the environment.

Claims

1. A method of quenching residual haloalkane in a nucleophilic polymerization reaction, characterized by, Under an inert atmosphere, a diacidic monomer and a dihalogenated monomer undergo a nucleophilic polymerization reaction, followed by the addition of a haloalkane for end-capping. After end-capping, an organic acid salt is added to the reactor and stirred to quench the reaction. The diacidic monomer is a diphenol or sulfur, selected from... , , , , , S, where n = 1 or 2; The dihalogenated monomer is selected from one or more of dihalogenated aromatic bisphthalimide or dihalogenated aromatic ketone sulfone compounds; The general structural formula of dihaloaromatic bisphthalimide is: Where X and Y represent F, Cl, Br, and I, respectively, and X and Y may be the same or different; A represents an aromatic group, selected from benzene rings and phenyl ether groups; the general structural formula of dihaloaryl ketone sulfones is: Where M and N represent F, Cl, Br, and I, respectively, and M and N may be the same or different; D represents... or ; The organic acid salt is a monobasic organic acid salt with 4 or fewer carbon atoms, and the organic acid salt is an alkali metal carboxylate. The molar ratio of the organic acid salt to the halogen in the haloalkane is 0.20 to 4.

0.

2. The method according to claim 1, characterized in that, Dibasic acidic monomers and dihalogenated monomers undergo polymerization in aprotic polar solvents.

3. The method according to claim 1, characterized in that, The polymerization reaction is carried out in the presence of an acid-binding agent and an optional co-catalyst.

4. The method according to claim 1, characterized in that, X and Y represent Br or Cl; A is selected from... , , ; where M and N represent F or Cl.

5. The method according to claim 1, characterized in that, The molar ratio of the diacidic monomer to the dihaloaromatic compound monomer is 1.05:1 to 1:1.

05.

6. The method according to claim 1, characterized in that, The gases used to create an inert atmosphere include one or more of nitrogen, argon, and helium.

7. The method according to claim 6, characterized in that, The gas used to create the inert atmosphere is nitrogen.

8. The method according to claim 2, characterized in that, The aprotic polar solvent includes one or more of sulfolane, N-methylpyrrolidone, N,N-dimethylacetamide, and dimethyl sulfoxide.

9. The method according to claim 3, characterized in that, The acid-binding agent is a basic compound selected from alkali metal hydroxides or alkali metal salts.

10. The method according to claim 9, characterized in that, The acid-binding agent is one or more of sodium hydroxide, potassium hydroxide, potassium carbonate, and sodium carbonate.

11. The method according to claim 10, characterized in that, The acid-binding agent is potassium carbonate or sodium hydroxide.

12. The method according to claim 3, characterized in that, The molar ratio of the basic functional group in the acid-binding agent to the acidic functional group or sulfur in the binary acidic monomer is 1:1 to 2:

1.

13. The method according to claim 3, characterized in that, The co-catalyst is an inorganic lithium salt or inorganic fluorine salt, selected from one or more of lithium chloride, lithium bromide, lithium carbonate, and potassium fluoride; the amount of the co-catalyst added is 0% to 1% of the molar amount of the dibasic acidic monomer.

14. The method according to claim 13, characterized in that, The amount of the co-catalyst added is 0.3~0.8% of the molar amount of the dibasic acidic monomer.

15. The method according to claim 1, characterized in that, The polymerization temperature is 166℃~240℃; the polymerization time is 2~20h.

16. The method according to claim 15, characterized in that, The polymerization temperature is 172~210℃; the polymerization time is 3~8h.

17. The method according to claim 1, characterized in that, The capping agent is a haloalkane with ≤3 carbon atoms.

18. The method according to claim 17, characterized in that, The number of halogen atoms in the capping agent is less than or equal to 3.

19. The method according to claim 18, characterized in that, The capping agent is selected from one or more of chloromethane, chloroethane, chloropropane, dichloromethane, trichloromethane, bromomethane, and bromoethane.

20. The method according to claim 19, characterized in that, The capping agent is selected from chloromethane or chloroethane.

21. The method according to claim 1, characterized in that, The molar ratio of halogen in the capping agent to acidic functional groups or sulfur in the binary acidic monomer is 1:100 to 6:

100.

22. The method according to claim 1, characterized in that, Before the haloalkane is capped, the temperature in the system is 166~240℃.

23. The method according to claim 22, characterized in that, Before the haloalkane is capped, the temperature in the system is 172~210℃.

24. The method according to claim 1, characterized in that, Before end capping, the solution is diluted and rapidly cooled by adding solvent.

25. The method according to claim 1, characterized in that, The end-capping reaction temperature is 140~210℃.

26. The method according to claim 25, characterized in that, The end-capping reaction temperature is 150~180℃.

27. The method according to claim 24, characterized in that, The solvents used for dilution include one or more of sulfolane, N-methylpyrrolidone, N,N-dimethylacetamide, and dimethyl sulfoxide.

28. The method according to claim 24, characterized in that, The solvent used for dilution is the same as the solvent used in the polymerization reaction.

29. The method according to claim 1, characterized in that, The organic acid salts include one or more of potassium formate, sodium formate, sodium acetate, potassium acetate, potassium butyrate, and sodium butyrate.

30. The method according to claim 1, characterized in that, The molar ratio of the organic acid salt to the halogen in the haloalkane is 0.25 to 1.

68.

31. The method according to claim 1, characterized in that, An aprotic polar solvent is also added during the quenching reaction. This aprotic polar solvent is the same as the one used in the polymerization reaction.

32. The method according to claim 31, characterized in that, In the quenching reaction, the amount of the aprotic polar solvent added is 2 to 15 times the mass of the organic acid salt.

33. The method according to claim 32, characterized in that, In the quenching reaction, the amount of the aprotic polar solvent added is 3 to 8 times the mass of the organic acid salt.

34. The method according to claim 1, characterized in that, An organic acid salt is added to carry out a quenching reaction at a temperature of 140~210℃ and a reaction time of 5min~180min.

35. The method according to claim 34, characterized in that, An organic acid salt is added to carry out a quenching reaction at a temperature of 150-180℃ for 20-60 minutes.

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