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研究了硝酸溶液中聚丙烯基聚偕氨肟(PPAO)—硫脲(TU)络合物引发丙烯腈(AN)聚合动力学。在[TU]/[PPAO]<0.5摩尔比的条件下,表观聚合速度(R_p)是R_p=9.1×10~4e~(-45.2k J/RT)[AN]~(2.0)[HNO_3]~(1.5)[TU]~(1.0)聚合物分子量随聚合温度升高而下降,并与硝酸浓度的1.5次方和硫脲浓度的1.0次方成反比,与丙烯腈浓度和 PPAO 浓度无关。可表示为_m=K·1/T·(1/[HNO_3]~(1.5)[TU]~(1.0))=K_M·1/T·(R_p/R_t)根据实验结果,提出了“络合—质子转移”引发机理。
Kinetics of polymerization of acrylonitrile (AN) initiated by PPAO-thiourea (TU) complex in nitric acid solution was studied. The apparent polymerization rate (R_p) is Rp = 9.1 × 10 -4 e ~ (-45.2 k J / RT) [AN] ~ (2.0) [HNO 3] under conditions of [TU] / [PPAO] The molecular weight of ~ (1.5) [TU] ~ (1.0) decreased with the increase of polymerization temperature and was inversely proportional to the 1.5th power of nitric acid concentration and the 1.0th power of thiourea concentration, independent of acrylonitrile concentration and PPAO concentration. Can be expressed as: _m = K · 1 / T · 1 / [HNO 3] -1.5 TU -1 1.0 = K_M · 1 / T · (R_p / R_t) According to the experimental results, Co-proton transfer "initiation mechanism.