| 杨梅形聚肟偕亚氨二乙酸钒(Ⅳ)—硫脲体系引发丙烯腈聚合的研究 |
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| 引用本文： | 吴锦远,杨超雄,杨义光.杨梅形聚肟偕亚氨二乙酸钒(Ⅳ)—硫脲体系引发丙烯腈聚合的研究[J].广州化学,1993(2). |
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| 作者姓名： | 吴锦远 杨超雄 杨义光 |
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| 作者单位： | 中国科学院广州化学研究所,中国科学院广州化学研究所,中国科学院广州化学研究所 |
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| 摘 要： | 研究了杨梅形聚肟偕亚氨二乙酸树脂负载VO~(2+)(PV)与疏脲(TU)组合在硝酸溶液中引发丙烯腈(AN)的聚合反应。在实验条件下,表观聚全速度可表示为 R_p=1.91×10~5e~(-45.0/RT)c~(1.9)(AN)c~(1.0)(HNO_3)c~(0.60)(PV)c~(1.50)(TU) 聚合诱导期(τ)与反应物浓度和聚合温度关系是 1/τ=8.27×10~7e~(-38.3/RT)c~(1.9)(HNO_3)c~(0.60)(PV)C~(1.50)(TU)=K_τ;·R_i/R_p 在酸性介质中,氨羧基的协同作用促使键合的VO~(2+)氧化为VO_2~+,随后硫脲配位并通过氢桥缔合,后者分解生成初级自由基,引发丙烯腈的聚合反应。
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KINETICS OF ACRYLONITRILE POLYMERIZATION INITIATED BY "ARBUTUS" VANADYL POLY (OXIME-IMIDODIACETATE) WITH THIOUREA COMBINATION |
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| Abstract: | The polymerization of acrylonitrile in aqueous nitric acid initiated by the system composed of "arbutus" vanadyl poly(oxime-imidodiacetate) and thiourea was investigated. The overall rate of polymerization may be written as R_p=1.91×10~8e~(-45.0/RT)c~(1.0)(AN)c~(1.0)(HNO_3)c~(0.6)(PV)c~(1.50)(TU) The relationship between the length of the induction period and the concentrations of reactants as well as the temperature of polymerization is 1/τ=8.27×10~7e~(-38.3/RT)c~(1.0)(HNO_3)c~(0.60)(PV)c~(1.50)(TU)=K_τ·R_i/R_p In acidic medium, the central ion, VO_2~+ of a polymeric complex is oxidized easily to VO_2~+ promoted by the synergy of the bonding imidodiacetic group. On which the thiourea coordinates and associates by hydrogen gridge. The latter decomposes and gives a primary radical ·S-C(NH_2)HH_2 to initiate the polymerization of acrylonitrile. |
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