A kind of graft with itaconic acid as skeleton and preparation method thereof
A technology of graft and itaconic acid, which is applied in the field of bio-based and biodegradable materials, can solve problems such as easy surface migration, easy phase separation, and limited compatibility improvement
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[0069] A preferred preparation method of the present invention is as follows, comprising steps:
[0070] (1) Monomethyl ester of itaconic acid. Itaconic acid, acid chloride reagent and dry methanol are mixed and heated to reflux state, after 30min-2h, cooled to room temperature. The crude product was recrystallized with a mixed solvent of petroleum ether to obtain product I (monomethyl β-itaconate).
[0071]
[0072] (2) Orthogonal protection of β-monomethyl itaconate. β-monomethyl itaconate reacts with di-tert-butyl pyrocarbonate (BOC2O) to protect the carboxyl group at the α position in the base 4-DMAT. The crude product was recrystallized from petroleum ether to obtain product II.
[0073]
[0074] (3) Demethylation of the product II in step (2). with MeOH:H 2 O=2:1, NaOH (2eq), heat to reflux for 1-4h, spin dry the solvent, extract, adjust the pH, extract with chloroform or dichloromethane, spin dry the solvent to obtain the demethylated product III.
[0075] ...
Embodiment 1
[0100] Add 0.10 mol of itaconic acid, 0.11 mol of dried methanol, and 60 mL of benzoyl chloride into a flask equipped with a reflux condenser and a sodium hydroxide solution gas absorption device. Heat the reaction liquid to reflux, slowly add benzoyl chloride dropwise, remove the heat when the hydrogen chloride gas is no longer discharged, cool to room temperature, remove the solvent by rotary evaporation and then distill under reduced pressure, collect 80-83°C fractions under 11mmHg pressure to obtain Product I (β-monomethyl itaconate).
Embodiment 2
[0102] Boc protection of β-monomethyl itaconate. 0.1 mol of β-monomethyl itaconate was dissolved in 50 mL of 4-DMAP as a solvent, and reacted with 0.06 mol of di-tert-butyl pyrocarbonate (BOC2O) under reflux for 3 hours to protect the carboxyl group at the α position. The crude product was recrystallized with petroleum ether, and the product II was obtained after drying.
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