| 聚丙烯基聚偕氨肟—硫脲络合物引发丙烯腈聚合动力学及机理 |
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| 引用本文： | 吴锦运,张广照,杨超雄.聚丙烯基聚偕氨肟—硫脲络合物引发丙烯腈聚合动力学及机理[J].广州化学,1992(1). |
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| 作者姓名： | 吴锦运 张广照 杨超雄 |
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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。
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MECHANISM FOR THE INITIATION OF ACRYLONITRILE POLYMERIZATION BY POLYPROPYLENE-BASED POLYAMIDOXIME-THIOUREA COMBINATION |
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| Abstract: | Polymerization of acrylonitriie(AN)in aqueous nitric acid initiated by polypropylene-based polyamidoxime(PPAO)-thiourea(TU)combination has been investigated.The overall rate of polymerization(R_p)under the conditions ofTU]/PPAO]<0.5 molar ratio is R_p=9.1×10~4e~(-45.2/R)AN]~(2.0)HNO_3]~(1.5)TU]~(1.0) The molecular weights of the polymers were found to be inversely proportional to 3/2-power of nitric acid concentration and l-power of thiourea concentration.In addition,it is independent with the concen trations of monomer and PPAO,and decreases with increasing temperature. On the basis of these experimental results,a coordination-proton transfer mechanism for the initiation was proposed and discussed. |
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