反应详情

To a solution of 2.52 g (2.93 mL, 14.5 mmol) of 1-methoxy-1-trimethylsiloxy-2-methyl-1-propene and 0.5 mL of tetrabutylammonium biacetate (0.1 M in propylene carbonate) in 40 mL of THF was added dropwise 29.8 g (33.7 mL, 189 mmol) of trimethylsilyl methacrylate (purified by passage over a column of basic alumina under argon). During the course of the addition the temperature of the reaction mixture rose from 26° C. to 32° C. When 0.5 mL of additional catalyst solution was added, the temperature rose to 50° C. When the temperature had fallen to 36° C., the addition of a mixture of 22.0 g (21.8 mL, 116 mmol) of 2-phenylethyl methacrylate (purified by passage over a column of basic alumina under argon) and 4.6 g (4.9 mL, 29 mmol) of 2-dimethylaminoethyl methacrylate (purified by distillation) was begun. An additional 0.5 mL of catalyst solution was added, and the temperature slowly rose from 34° C. to 36° C. During 30 min, the temperature fell to 30° C. Then 14.5 g (14.5 mL, 58.2 mmol) of ethoxytriethylene glycol methacrylate (purified by passage over a column of basic alumina under argon) was added dropwise from an addition funnel. An additional 0.5 mL of catalyst solution was added, and during 40 min, the temperature rose to 32° C. and then fell to room temperature. Analysis of an aliquot of the solution by 1H nmr showed that there was no residual monomer present. The solution of poly(trimethylsilyl methacrylate [48 mol %]-b-2-phenylethyl methacrylate [30 mol %]-co-2-dimethylaminoethyl methacrylate [7 mol %]-b-ethoxytriethylene glycol methacrylate [15 mol %]) was treated with 45 mL of 0.03 M methanolic tetrabutylammonium fluoride and heated at reflux for 8 hr. The solution was evaporated in a rotary evaporator under reduced pressure. The residual polymer was dried for 24 hr in a vacuum oven to give 59 g of poly(methacrylic acid [48 mol %]-b-2-phenylethyl methacrylate [30 mol %]-co-2-dimethylaminoethyl methacrylate [7 mol %]-b-ethoxytriethylene glycol methacrylate [15 mol% ]). 1H NMR analysis of the product showed that no trimethylsilyl ester groups remained.

1. custompurified by passage over a column of basic alumina under argon)
2. additionDuring the course of the addition the temperature of the reaction mixture
3. customrose from 26° C. to 32° C
4. additionWhen 0.5 mL of additional catalyst solution was added
5. customrose to 50° C
6. customhad fallen to 36° C.
7. customslowly rose from 34° C. to 36° C
8. customfell to 30° C
9. additionwas added dropwise from an addition funnel
10. waitduring 40 min
11. customrose to 32° C.
12. customfell to room temperature
13. temperatureheated
14. temperatureat reflux for 8 hr
15. customThe solution was evaporated in a rotary evaporator under reduced pressure
16. customThe residual polymer was dried for 24 hr in a vacuum oven