在水溶液中腈纶偕胺肟化反应的研究

A Study of Amidoximation or Polyacrylonitrile Fibre in Aqueous Solution

本文指出腈纶与加碳酸钠的硫酸羟胺水溶液的偕胺肟化反应实质上是腈纶中氰基与羟胺之间的反应，属于碳－杂重键的亲电加成反应。非均相偕胺肟化反应的动力学方程为Ｒ＝ｋ［Ｈ２ＮＯＨ］０．７９１（ｍｍｏｌ／ｇ．ｓ），７０℃时ｋ＝４．９７×１０－４（ｍｍｏｌ．Ｌ／ｍｏｌ．ｇ．ｓ）。表观反应活化能低于和高于６５℃分别为２６８．７和 ２９２．０ＫＪ／ｍｏｌ。

It has been indicated that the amidoximation reaction of polyacrylonitle fibre in an acueous solution of hydroxylammonium sulfate added to with sodium carbonate essentially is the reaction of nitrile group in acrylics with hydroxylamine,i. e. an electrophilic additional reaction of multiple linkage between carbon and other atoms. The kinetic equation of the reaction in a heterogenious phase can be described as R = K (H2NOH)0.791 (mmol/g. s)with the constant of the reaction rate K = 4. 9 × 10-4 (mmol. L/mol. g. s) at 70℃. The apparent active energy of the reaction is 268. 7KJ/mol below 65℃ and 292. 0KJ/mol above 65℃ respectively.