反应详情

温度

70 °C

In a nitrogen atmosphere, a 300 mL four-neck flask was charged with 30 g (0.113 mol) of 1,3,5-benzenetricarbonyl trichloride (Tokyo Chemical Industry) and 133.3 g of N-methyl-2-pyrrolidone (abbreviated below as “NMP”; Junsei Chemical Co., Ltd.), following which a solution of 9.16 g (84.8 mmol) of 1,3-phenylenediamine (DuPont K.K.) and 7.89 g (84.8 mmol) of aniline (Junsei Chemical Co., Ltd.) dissolved in 133.3 g of NMP (Junsei Chemical Co., Ltd.) was added dropwise over a period of 30 minutes at an internal temperature of 0 to 5° C. Following the completion of dropwise addition, the flask contents were stirred for 30 minutes at a temperature of 10° C. or below. A solution of 12.73 g (169.5 mmol) of DL-1-amino-2-propanol (Tokyo Chemical Industry) dissolved in 90 g of NMP (Junsei Chemical Co., Ltd.) was added dropwise to this at an internal temperature of from −3 to −1° C. over a period of 30 minutes, following which the temperature was raised to 70° C. and stirring was carried out for 2 hours. The reaction mixture was added to 3,000 g of pure water to effect re-precipitation and the resulting precipitate was collected by filtration, then dried at 150° C. for 3 hours in a vacuum desiccator. The resulting moist product was again dissolved in 180 g of N,N-dimethylacetamide (abbreviated below as “DMAc”) and stirred at 55° C. for 1 hour. Next, the DMAc solution was allowed to cool to 30° C., then added to 600 g of pure water heated to 50° C. and re-precipitated, followed by stirring at 50° C. for 1 hour. After allowing the contents to cool to 30° C., filtration was carried out and the filtrate was dried in a vacuum desiccator at 150° C. for 10 hours, giving 35.85 g of the target tricarbonylbenzene-based hyperbranched polymer (abbreviated below as “HPmDAP”). FIG. 1 shows the 1H-NMR spectrum obtained for HPmDAP.

1. additionwas added dropwise over a period of 30 minutes at an internal temperature of 0 to 5° C
2. additionthe completion of dropwise addition
3. additionwas added dropwise to this at an internal temperature of from −3 to −1° C. over a period of 30 minutes
4. stirringstirring
5. waitwas carried out for 2 hours
6. customre-precipitation
7. filtrationthe resulting precipitate was collected by filtration
8. customdried at 150° C. for 3 hours in a vacuum desiccator
9. dissolutionThe resulting moist product was again dissolved in 180 g of N,N-dimethylacetamide (
10. stirringstirred at 55° C. for 1 hour
11. temperatureto cool to 30° C.
12. additionadded to 600 g of pure water
13. temperatureheated to 50° C.
14. customre-precipitated
15. stirringby stirring at 50° C. for 1 hour
16. temperatureto cool to 30° C.
17. filtrationfiltration
18. customthe filtrate was dried in a vacuum desiccator at 150° C. for 10 hours