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研究了杨梅型聚丙烯基亚氨二乙酸钒(PIDA/VO)—硫脲(TU)体系在硫酸溶液中引发丙烯腈聚合动力学。表观聚合速度(Rp)和聚合物分子量(Mn)可分别表示为: Rp=2.2×10~5e~(-0860)/RT[AN]~1.0[PV]~0.50[TU]~1.5[H_2SO_4]~2.0 Mn=K·1/T·[AN]/[PV]~0.50[TU]~1.5[H_2SO_4]~2.0其中([PV]~0.05[TU]~1.5[H_2SO_4]~2.0)~2是正比于引发种浓度。由此可见,链自由基是以双基反应终止,伯基终止及链转移终止的可能性较少。和聚羧酸钒(Ⅳ)—硫脲体系引发丙烯腈聚合的机理相同,杨梅型聚丙烯基亚氨二乙酸钒(Ⅳ)也表现出强烈的羧基间协同作用和大分子场效应。
The polymerization kinetics of acrylonitrile initiated by the mycelium of propylene-propyleneimine diacetate (PIDA / VO) -thiourea (TU) system in sulfuric acid solution was studied. The apparent polymerization rate (Rp) and the molecular weight (Mn) of the polymer can be expressed as Rp = 2.2 × 10-5e -0860 / RT [AN] ~ 1.0 [PV] ~ 0.50 [TU] -1.5 [H_2SO_4 ] ~ 2.0 Mn = K · 1 / T · [AN] / [PV] ~ 0.50 [TU] ~ 1.5 [H_2SO_4] ~ 2.0 where [PV] ~ 0.05 [TU] ~ 1.5 [H_2SO_4] ~ 2.0) ~ 2 Is proportional to the trigger species concentration. Thus, the chain free radical is terminated by a double base reaction, Burke termination and chain transfer less likely to terminate. The mechanism of polymerization of acrylonitrile was the same as that of vanadium (IV) -carboxylate-thiourea system. The vanadium (IV) of bayberry-type poly (propyleneimine) diacetate also showed strong synergistic effect between carboxyl groups and macromolecule field effect.