反应详情

To a solution of 5.55 g (6.31 mL, 24 mmol) of 1-(2-dimethylaminoethoxy)-1-trimethylsiloxy-2-methyl-1-propene and 0.1 mL of tetrabutylammonium biacetate (0.04M in propylene carbonate) in 30 mL of THF was added a mixture of 7.6 g (8.1 mL, 48 mmol) of 2-dimethylaminoethyl methacrylate (purified by passage over a column of basic alumina under argon), and 23.9 g (26.7 mL, 168 mmol) of n-butyl methacrylate (purified by passage over a column of basic alumina under argon) from an addition funnel. The temperature of the reaction mixture rose from 27° C. to 61° C. during the course of the addition, and an ice bath was used to moderate the temperature rise. When, following the conclusion of the addition and removal of the cooling bath, the temperature was 32° C., the dropwise addition of 49.4 g (56.1 mL, 312 mmol) of trimethylsilyl methacrylate was begun. During the course of the addition the temperature of the reaction mixture rose to 56° C. while a total of 1.2 mL of tetrabutylammonium biacetate (0.04M in propylene carbonate) was added in 4 additions, and 20 mL of THF was added to reduce viscosity. Analysis of an aliquot of the solution by 1H NMR showed that there was no residual monomer present. After addition of 70 mL of tetrabutylammonium fluoride trihydrate (0.03M in methanol), the solution was refluxed for 12 hr. The solution was concentrated under reduced pressure with a rotary evaporator to give 80 g of a 40.58% solids solution of poly ω-2-β-dimethylaminoethyl isobutyrate(2-dimethylaminoethyl methacrylate [9 mol %]-co-n-butyl methacrylate [32 mol %]-b-methacrylic acid [59 mol %]).

1. custompurified by passage over a column of basic alumina under argon) from an addition funnel
2. additionThe temperature of the reaction mixture rose from 27° C. to 61° C. during the course of the addition, and an ice bath
3. additionthe conclusion of the addition and removal of the cooling bath
4. customwas 32° C.
5. additionDuring the course of the addition the temperature of the reaction mixture
6. additionwas added
7. temperaturethe solution was refluxed for 12 hr
8. concentrationThe solution was concentrated under reduced pressure with a rotary evaporator