Citation:
XU Miao-Qing, HUANG Jian-Ying, YAN Ming-Fa, LIN Qiang, LIN Ming-Hua, CHEN Yi-Hong, ZOU You-Si. The Rate-accelerating Additives for Living Free radical Polymerization of Styrene in the Presence of Sodium Nitrite and Iron(Ⅱ) Sulfate[J]. Chinese Journal of Applied Chemistry,
;2005, 22(9): 1017-1020.
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The rate-accelerating additives for living free radical polymerization of styrene in the presence of sodium nitrite and iron(Ⅱ) sulfate were studied.It was found that the styrene polymerization mediated with AIBN/NaNO2/FeSO4·7H2O was distinctly accelerated by the additive,such as diethylmalonate(DEM),acetylacetone(AAT),ethyl acetoacetic ester(AAE),or malonoitrile(MN).Among those additives,(malonoitrile)(MN) showed the best effect of rate enhancement and maintained the character of living free-radical polymerization while accelerating the rate of the polymerization.The conversion reached 80.0% within 5 h at 120℃ when n(MN):n(NaNO2):n(FeSO4·7H2O)=4:1:1 and [MN] equaled 0.312 mol/L.The polymerization rate was twenty times as fast as that of the polymerization without any additives.The molecular weight distribution was narrow,and the molecular weight was well controlled under 4×104,and the difference between the theoretical molecular weight and the experimental molecular weight was below 20%.With the increase of the conversion of monomer,the molecular weight of the polymer also increased linearly.The spectrum of 1H NMR show that MN didn't alter the structure of the polymer and only acted as an accelerator.
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