Meta-stable state nitrogen-containing polymer

Firstly, oligomer of phenylmethane maleimide (Compound (A)) was dissolved in EC/PC in an amount of 3%, to form a mixture solution. Next, 2,4-dimethyl-2-imidazoline (Compound (B)) was added into the mixture solution in batches, for thermal polymerization at 130° C. for 8 hours, so as to obtain a meta-stable state nitrogen-containing polymer of Example 1. The molar ratio of 3% oligomer of phenylmethane maleimide to 2,4-dimethyl-2-imidazoline was 2:1.

The meta-stable state nitrogen-containing polymer of Example 1 was a narrow polydispersity polymer having a GPC peak time of 20.5 min and a PDI of 1.2, as shown in FIG. 1 . Furthermore, the meta-stable state nitrogen-containing polymer of Example 1 was re-induced to react at a temperature of 186° C., to convert the meta-stable state nitrogen-containing polymer into a macromolecular polymer completely. Polydispersity index (PDI) is defined as weight average molecular weight divided by number average molecular weight (Mw/Mn).

Firstly, 4,4′-diphenylmethane bismaleimide (Compound (A)) was dissolved in GBL in an amount of 5%, to form a mixture solution. Next, 2,4-dimethyl-2-imidazoline (Compound (B)) was added into the mixture solution in batches, for thermal polymerization at 100° C. for 15 hours, so as to obtain a meta-stable state nitrogen-containing polymer of Example 2. The molar ratio of 5% 4,4′-diphenylmethane bismaleimide to 2,4-dimethyl-2-imidazoline was 2:1.

The meta-stable state nitrogen-containing polymer of Example 2 was a narrow polydispersity polymer having a GPC peak time of 22.4 min and a PDI of 1.2, as shown in FIG. 2 . Furthermore, the meta-stable state nitrogen-containing polymer of Example 2 was re-induced to react at a temperature of 180° C., to convert the meta-stable state nitrogen-containing polymer into a macromolecular polymer completely.

Firstly, oligomer of phenylmethane maleimide (Compound (A)) was dissolved in NMP in an amount of 3%, to form a mixture solution. Next, 2,4-dimethyl-2-imidazoline (Compound (B)) was added into the mixture solution in batches, for thermal polymerization at 150° C. for 3 hours, so as to obtain a meta-stable state nitrogen-containing polymer of Example 3. The molar ratio of 3% oligomer of phenylmethane maleimide to 2,4-dimethyl-2-imidazoline was 4:1.

The meta-stable state nitrogen-containing polymer of Example 3 was a narrow polydispersity polymer having a GPC peak time of 22.6 min and a PDI of 1.2, as shown in FIG. 3 . Furthermore, the meta-stable state nitrogen-containing polymer of Example 3 was re-induced to react at a temperature of 186° C., to convert the meta-stable state nitrogen-containing polymer into a macromolecular polymer completely.

Firstly, 4,4′-diphenylmethane bismaleimide (Compound (A)) was dissolved in NMP in an amount of 3%, to form a mixture solution. Next, imidazole (Compound (B)) was added into the mixture solution in batches, for thermal polymerization at 130° C. for 8 hours, so as to obtain a meta-stable state nitrogen-containing polymer of Example 4. The molar ratio of 3% 4,4′-diphenylmethane bismaleimide to imidazole was 4:1.

The meta-stable state nitrogen-containing polymer of Example 4 was a narrow polydispersity polymer having a GPC peak time of 22.8 min and a PDI of 1.3, as shown in FIG. 4 . Furthermore, the meta-stable state nitrogen-containing polymer of Example 4 was re-induced to react at a temperature of 200° C., to convert the meta-stable state nitrogen-containing polymer into a macromolecular polymer completely.

Firstly, 1,6′-bismaleimide-(2,2,4-trimethyl)hexane (Compound (A)) was dissolved in GBL in an amount of 3%, to form a mixture solution. Next, pyridazine (Compound (B)) was added into the mixture solution in batches, for thermal polymerization at 100° C. for 12 hours, so as to obtain a meta-stable state nitrogen-containing polymer of Example 5. The molar ratio of 3% 1,6′-bismaleimide-(2,2,4-trimethyl)hexane to pyridazine was 2:1.

The meta-stable state nitrogen-containing polymer of Example 5 was a narrow polydispersity polymer having a GPC peak time of 22.2 min and a PDI of 1.5, as shown in FIG. 5 . Furthermore, the meta-stable state nitrogen-containing polymer of Example 5 was re-induced to react at a temperature of 190° C., to convert t the meta-stable state nitrogen-containing polymer into a macromolecular polymer completely.

Firstly, 2,2′-bis[4-(4-maleimidophenoxy)phenyl]propane (Compound (A)) was dissolved in GBL in an amount of 3%, to form a mixture solution. Next, pyridine (Compound (B)) was added into the mixture solution in batches, for thermal polymerization at 60° C. for 24 hours, so as to obtain a meta-stable state nitrogen-containing polymer of Example 6. The molar ratio of 3% 2,2′-bis[4-(4-maleimidophenoxy)phenyl]propane to pyridine was 4:1.

The meta-stable state nitrogen-containing polymer of Example 6 was a narrow polydispersity polymer having a GPC peak time of 19 min and a PDI of 1.2, as shown in FIG. 6 . Furthermore, the meta-stable state nitrogen-containing polymer of Example 6 was re-induced to react at a temperature of 180° C., to convert the meta-stable state nitrogen-containing polymer into a macromolecular polymer completely.

Firstly, oligomer of phenylmethane maleimide (Compound (A)) was dissolved in EC/PC in an amount of 5%, to form a mixture solution. Next, 2,4,6-triamino-1,3,5,-triazine (Compound (B)) was added into the mixture solution in batches, for thermal polymerization at 130° C. for 12 hours, so as to obtain a meta-stable state nitrogen-containing polymer of Example 7. The molar ratio of 5% oligomer of phenylmethane maleimide to 2,4,6-triamino-1,3,5,-triazine was 2:1.

The meta-stable state nitrogen-containing polymer of Example 7 was a narrow polydispersity polymer having a GPC peak time of 20.1 min and a PDI of 1.1, as shown in FIG. 7 . Furthermore, the meta-stable state nitrogen-containing polymer of Example 7 was re-induced to react at a temperature of 190° C., to convert the meta-stable state nitrogen-containing polymer into a macromolecular polymer completely.

Firstly, oligomer of phenylmethane maleimide (Compound (A)) was dissolved in EC/PC in an amount of 5%, to form a mixture solution. Next, 2,4-dimethyl-2-imidazoline (Compound (B)) was added into the mixture solution in batches, for thermal polymerization at 80° C. for 18 hours, so as to obtain a meta-stable state nitrogen-containing polymer of Example 8. The molar ratio of 5% oligomer of phenylmethane maleimide to 2,4-dimethyl-2-imidazoline was 10:1.

The meta-stable state nitrogen-containing polymer of Example 8 was a narrow polydispersity polymer having a GPC peak time of 20.5 min and a PDI of 1.5, as shown in FIG. 8 . Furthermore, the meta-stable state nitrogen-containing polymer of Example 8 was re-induced to react at a temperature of 170° C., to convert the meta-stable state nitrogen-containing polymer into a macromolecular polymer completely.

Firstly, 2,2′-bis[4-(4-maleimidophenoxy)phenyl]propane (Compound (A)) was dissolved in GBL in an amount of 5%, to form a mixture solution. Next, 4-tert-butylpyridine (Compound (B)) was added into the mixture solution in batches, for thermal polymerization at 60° C. for 24 hours, so as to obtain a meta-stable state nitrogen-containing polymer of Example 9. The molar ratio of 5% 2,2′-bis[4-(4-maleimidophenoxy)phenyl]propane to 4-tert-butylpyridine was 4:1.

The meta-stable state nitrogen-containing polymer of Example 9 was a narrow polydispersity polymer having a GPC peak time of 20 min and a PDI of 1.5, as shown in FIG. 9 . Furthermore, the meta-stable state nitrogen-containing polymer of Example 9 was re-induced to react at a temperature of 120° C., to convert the meta-stable state nitrogen-containing polymer into a macromolecular polymer completely.

Firstly, 4,4′-diphenylmethane bismaleimide and 2,2-bis(4-(p-maleimidophenoxy)-phenyl)-hexafluoropropane in a molar ratio of 4:1 were dissolved in EC/PC, to form a 3% mixture solution. Next, 2,4-dimethyl-2-imidazoline was added into the mixture solution in batches, for thermal polymerization at 130° C. for 8 hours, so as to obtain a meta-stable state nitrogen-containing polymer of Example 10. The molar ratio of 3% mixture solution to 2,4-dimethyl-2-imidazoline was 2:1.

The meta-stable state nitrogen-containing polymer of Example 10 was a narrow polydispersity polymer having a GPC peak time of 23.1 min and a PDI of 1.5, as shown in FIG. 10 . Furthermore, the meta-stable state nitrogen-containing polymer of Example 10 was re-induced to react at a temperature of 200° C., to convert the meta-stable state nitrogen-containing polymer into a macromolecular polymer completely.

Firstly, 4,4′-diphenylmethane bismaleimide and 2,2-bis(4-(p-maleimidophenoxy)-phenyl)-hexafluoropropane in a molar ratio of 2:1 were dissolved in EC/PC, to form a 3% mixture solution. Next, 2,4-dimethyl-2-imidazoline was added into the mixture solution in batches, for thermal polymerization at 130° C. for 8 hours, so as to obtain a meta-stable state nitrogen-containing polymer of Example 11. The molar ratio of 3% mixture solution to 2,4-dimethyl-2-imidazoline was 2:1.

The meta-stable state nitrogen-containing polymer of Example 11 was a narrow polydispersity polymer having a GPC peak time of 23.7 min and a PDI of 1.5, as shown in FIG. 11 . Furthermore, the meta-stable state nitrogen-containing polymer of Example 11 was re-induced to react at a temperature of 205° C., to convert the meta-stable state nitrogen-containing polymer into a macromolecular polymer completely.

Firstly, 4,4′-diphenylmethane bismaleimide and 1,8-bis-maleimidodiethylene glycol in a molar ratio of 2:1 were dissolved in EC/PC, to form a 3% mixture solution. Next, 2,4-dimethyl-2-imidazoline was added into the mixture solution in batches, for thermal polymerization at 130° C. for 8 hours, so as to obtain a meta-stable state nitrogen-containing polymer of Example 12. The molar ratio of 3% mixture solution to 2,4-dimethyl-2-imidazoline was 2:1.

The meta-stable state nitrogen-containing polymer of Example 12 was a narrow polydispersity polymer having a GPC peak time of 19.3 min and a PDI of 1.5, as shown in FIG. 12 . Furthermore, the meta-stable state nitrogen-containing polymer of Example 12 was re-induced to react at a temperature of 180° C., to convert the meta-stable state nitrogen-containing polymer into a macromolecular polymer completely.

Firstly, tris(2-maleimidoethyl)amine and 2,2-bis(4-(p-maleimidophenoxy)-phenyl)-hexafluoropropane in a molar ratio of 2:1 were dissolved in EC/PC, to form a 3% mixture solution. Next, 2,4-dimethyl-2-imidazoline was added into the mixture solution in batches, for thermal polymerization at 130° C. for 4 hours, so as to obtain a meta-stable state nitrogen-containing polymer of Example 13. The molar ratio of 3% mixture solution to 2,4-dimethyl-2-imidazoline was 2:1.

The meta-stable state nitrogen-containing polymer of Example 13 was a narrow polydispersity polymer having a GPC peak time of 20.2 min and a PDI of 1.1, as shown in FIG. 13 . Furthermore, the meta-stable state nitrogen-containing polymer of Example 13 was re-induced to react at a temperature of 160° C., to convert the meta-stable state nitrogen-containing polymer into a macromolecular polymer completely.

Firstly, 1,8-bis-maleimidodiethylene glycol and 2,2-bis(p-maleimidophenyl)-hexafluoropropane in a molar ratio of 4:1 were dissolved in EC/PC, to form a 3% mixture solution. Next, 2,4-dimethyl-2-imidazoline was added into the mixture solution in batches, for thermal polymerization at 120° C. for 6 hours, so as to obtain a meta-stable state nitrogen-containing polymer of Example 14. The molar ratio of 3% mixture solution to 2,4-dimethyl-2-imidazoline was 2:1.

The meta-stable state nitrogen-containing polymer of Example 14 was a narrow polydispersity polymer having a GPC peak time of 23.2 min and a PDI of 1.2, as shown in FIG. 14 . Furthermore, the meta-stable state nitrogen-containing polymer of Example 14 was re-induced to react at a temperature of 220° C., to convert the meta-stable state nitrogen-containing polymer into a macromolecular polymer completely.

Firstly, 4,4′-diphenylether bismaleimide and 2,2-bis(4-(p-maleimidophenoxy)-phenyl)-hexafluoropropane in a molar ratio of 4:1 were dissolved in EC/PC, to form a 3% mixture solution. Next, 2,4-dimethyl-2-imidazoline was added into the mixture solution in batches, for thermal polymerization at 100° C. for 15 hours, so as to obtain a meta-stable state nitrogen-containing polymer of Example 15. The molar ratio of 3% mixture solution to 2,4-dimethyl-2-imidazoline was 2:1.

The meta-stable state nitrogen-containing polymer of Example 15 was a narrow polydispersity polymer having a GPC peak time of 20.2 min and a PDI of 1.1, as shown in FIG. 15 . Furthermore, the meta-stable state nitrogen-containing polymer of Example 15 was re-induced to react at a temperature of 185° C., to convert the meta-stable state nitrogen-containing polymer into a macromolecular polymer completely.

Firstly, 4,4′-diphenylsulfone bismaleimide and 2,2-bis(4-(p-maleimidophenoxy)-phenyl)-hexafluoropropane in a molar ratio of 4:1 were dissolved in EC/PC, to form a 3% mixture solution. Next, 2,4-dimethyl-2-imidazoline was added into the mixture solution in batches, for thermal polymerization at 130° C. for 8 hours, so as to obtain a meta-stable state nitrogen-containing polymer of Example 16. The molar ratio of 3% mixture solution to 2,4-dimethyl-2-imidazoline was 2:1.

The meta-stable state nitrogen-containing polymer of Example 16 was a narrow polydispersity polymer having a GPC peak time of 21 min and a PDI of 1.6, as shown in FIG. 16 . Furthermore, the meta-stable state nitrogen-containing polymer of Example 16 was re-induced to react at a temperature of 180° C., to convert the meta-stable state nitrogen-containing polymer into a macromolecular polymer completely.

Firstly, 1,3-bis(3-maleimidophenoxy)benzene and 2,2-bis(4-(p-maleimidophenoxy)-phenyl)-hexafluoropropane in a molar ratio of 4:1 were dissolved in EC/PC, to form a 3% mixture solution. Next, 2,4-dimethyl-2-imidazoline was added into the mixture solution in batches, for thermal polymerization at 130° C. for 8 hours, so as to obtain a meta-stable state nitrogen-containing polymer of Example 17. The molar ratio of 3% mixture solution to 2,4-dimethyl-2-imidazoline was 2:1.

The meta-stable state nitrogen-containing polymer of Example 17 was a narrow polydispersity polymer having a GPC peak time of 20.5 min and a PDI of 1.6, as shown in FIG. 17 . Furthermore, the meta-stable state nitrogen-containing polymer of Example 17 was re-induced to react at a temperature of 205° C., to convert the meta-stable state nitrogen-containing polymer into a macromolecular polymer completely.

Firstly, tris(2-maleimidoethyl)amine was dissolved in EC/PC in an amount of 3%, to form a mixture solution. Next, 2,4-dimethyl-2-imidazoline was added into the mixture solution in batches, for thermal polymerization at 130° C. for 8 hours, so as to obtain a meta-stable state nitrogen-containing polymer of Example 18. The molar ratio of 3% tris(2-maleimidoethyl)amine to 2,4-dimethyl-2-imidazoline 2:1.

The meta-stable state nitrogen-containing polymer of Example 18 was a narrow polydispersity polymer having a GPC peak time of 21.3 min and a PDI of 1.2, as shown in FIG. 18 . Furthermore, the meta-stable state nitrogen-containing polymer of Example 9 was re-induced to react at a temperature of 195° C., to convert the meta-stable state nitrogen-containing polymer into a macromolecular polymer completely.

Firstly, 1,8-bis-maleimidodiethylene glycol and 4-maleimido-benzenesufonic acid in a molar ratio of 4:1 were dissolved in EC/PC, to form a 3% mixture solution. Next, 2,4-dimethyl-2-imidazoline was added into the mixture solution in batches, for thermal polymerization at 130° C. for 8 hours, so as to obtain a meta-stable state nitrogen-containing polymer of Example 19. The molar ratio of 3% mixture solution to 2,4-dimethyl-2-imidazoline was 2:1.

The meta-stable state nitrogen-containing polymer of Example 19 was a narrow polydispersity polymer having a GPC peak time of 22.5 min and a PDI of 1.3, as shown in FIG. 19 . Furthermore, the meta-stable state nitrogen-containing polymer of Example 19 was re-induced to react at a temperature of 198° C., to convert the meta-stable state nitrogen-containing polymer into a macromolecular polymer completely.

Firstly, 1,8-bis-maleimidodiethylene glycol and 2,2-bis(4-(p-maleimidophenoxy)-phenyl)-hexafluoropropane in a molar ratio of 4:1 were dissolved in GBL, to form a 3% mixture solution. Next, 2,4-dimethyl-2-imidazoline was added into the mixture solution in batches, for thermal polymerization at 120° C. for 8 hours, so as to obtain a meta-stable state nitrogen-containing polymer of Example 20. The molar ratio of 3% mixture solution to 2,4-dimethyl-2-imidazoline was 2:1.

The meta-stable state nitrogen-containing polymer of Example 20 was a narrow polydispersity polymer having a GPC peak time of 20.5 min and a PDI of 1.3, as shown in FIG. 20 . Furthermore, the meta-stable state nitrogen-containing polymer of Example 20 was re-induced to react at a temperature of 202° C., to convert the meta-stable state nitrogen-containing polymer into a macromolecular polymer completely.

Firstly, tris(2-maleimidoethyl)amine and 4-maleimidophenol in a molar ratio of 2:1 were dissolved in GBL, to form a 3% mixture solution. Next, 4-tert-butylpyridine was added into the mixture solution in batches, for thermal polymerization at 110° C. for 6 hours, so as to obtain a meta-stable state nitrogen-containing polymer of Example 21. The molar ratio of 3% mixture solution to 4-tert-butylpyridine was 2:1.

The meta-stable state nitrogen-containing polymer of Example 21 was a narrow polydispersity polymer having a GPC peak time of 19 min and a PDI of 1.1, as shown in FIG. 21 . Furthermore, the meta-stable state nitrogen-containing polymer of Example 21 was re-induced to react at a temperature of 175° C., to convert the meta-stable state nitrogen-containing polymer into a macromolecular polymer completely.

Table 3 summaries synthesis conditions and experimental results of Examples 1-21.

Furthermore, GPC stability test and viscosity stability test were also performed on the meta-stable state nitrogen-containing polymer of Example 3, as shown in FIGS. 22-23 . Referring to FIG. 22 , the meta-stable state nitrogen-containing polymer of Example 3 was stored at 55° C. for 1 month, wherein the PDI of the first day is 1.2, and the PDI of the 30 th day is 1.21, and the variance of PDI of the meta-stable state nitrogen-containing polymer of Example 3 is lower than 2% after being stored at 55° C. for 1 month. Referring to FIG. 23 , the meta-stable state nitrogen-containing polymer of Example 3 was stored at 55° C. for 1 month, wherein the viscosity of the first day is 6.2 cP, and the viscosity of the 30 th day is 6.3 cP, and the variance of viscosity of the meta-stable state nitrogen-containing polymer of Example 3 is lower than 2% after being stored at 55° C. for 1 month.

In the above embodiments, Compound (B) is described with a heterocyclic amino aromatic derivative as a nucleophilic initiator as an example; however, the disclosure is not limited thereto. Persons of ordinary skill in the art should appreciate that, Compound (B) may also be a tertiary amine or a secondary amine, which is reacted with Compound (A) (that is, a monomer with a reactive terminal functional group), to generate a meta-stable state nitrogen-containing polymer.

In summary, the meta-stable state nitrogen-containing polymer of the disclosure has the advantages of both “two-liquid type” and “one-liquid type” polymers but without the drawbacks of the same. In details, the meta-stable state nitrogen-containing polymer of the disclosure does not require a mixing step and can be stored at room temperature (or above room temperature) for a long period of time, and the viscosity thereof will not change drastically after unsealing.

Furthermore, the meta-stable state nitrogen-containing polymer of the disclosure has part of the functional groups remained, which is beneficial to the subsequent processing, and optionally, the remaining reactive function groups may be facilitated to react by heating or applying a voltage. The application of the meta-stable state nitrogen-containing polymer of the disclosure is wide, such as an electrolyte additive of a secondary battery, a water-keeping layer of a fuel cell, a solid electrolyte, etc.

It will be apparent to those skilled in the art that various modifications and variations can be made to the structure of the disclosed embodiments without departing from the scope or spirit of the disclosure. In view of the foregoing, it is intended that the disclosure cover modifications and variations of this disclosure provided they fall within the scope of the following claims and their equivalents.