Syntheses and Polymerizations of Acrylates from Keto Alcohols and Chlorinated Alcohols

Abstract

2-Oxocyclohexyl acrylate, phenacyl acrylate, α-trichloromethyl-β-carbomethoxyethyl acrylate and β, β, β-trichloroisopropyl acrylate have been prepared readily by the condensation of acryloyl chloride and the corresponding alcohol with the aid of triethylamine (equation A).
CH₂=CHCOCl + ROH N (C₂H₅)₃→ CH₂=CHCOOR (A)
R=-H=O -CH₂CO-_??_
-CHCH₂COOCH₃-CCl₃, -CHCH₃-CCl₃
By the alcoholysis of methyl acrylate and methyl methacrylate with 2, 4, 4, 4-tetrachlorobutanol-1, 2, 4, 4, 4-tetrachlorobutyl acrylate and 2, 4, 4, 4-tetrachlorobutyl methacrylatehave also been prepared (equation B).
CH₂=CR'COOCH₃ + ROH H₂SO₄→ CH₂=CR'COOR (B)
R=-CH₂CHCH₂CCl₃-Cl, R'=H
R=-CH₂CHCH₂CCl₃-Cl, R'=CH₃
These new acrylates and methacrylate have been polymerized in dioxane using 2, 2'-azobisisobutyronitrile as an initiator.
Among others, the Polyacrylates and the polymethacrylates having three to four chlorine atoms in one unit of the polymer chain give films which do not burn.