Vinyl polymerization, 265. Polymerization of methyl methacrylate initiated with nylon‐6 and water in the absence or presence of carbon tetrachloride. Contribution of a trace amount of cupric ion to the polymerization.

Polymerization of methly methacrylate (MMA) was carried out in the presence of nylon‐6 with different content of amino end groups and water. The more the content of amino end groups of the nylon molecule, the lower is the conversion of MMA. The rate of polymerization, Rp, is proportional to the amount of nylon. However, as for the amount of MMA, the rate increased at first amount of MMA, but then became independent of the amount of MMA. These kinetical behaviours suggest a model of an enzyme‐like reaction. MICHAELIS‐MENTEN'S equation was found to be able adequately to be applied. The polymerization was confirmed to proceed through a radical mechanism. By the activation analysis, it was found that the nylon used here contained a slight amount of copper (5 – 8 · 10−7 g Cu/g fiber). When the nylon was dissolved in formic acid and reprecipitated by adding hot water, the nylon was found to lose the activity for the polymerization. However, when a trace of CuCl2 was absorbed on the nylon, the nylon was confirmed to regain the activity. As a conclusion, an assumed mechanism similar to an enzymatic reaction in which nylon plays as enzyme and copper as coenzyme was proposed. In the second part of the present paper, a study on the polymerization in the presences of carbon tetrachloride was made. Regardless of the content of the NH2− end groups, the conversion was always near to quantitative yield. The mechanism was found to be a radical one. An initiation mechanism, in which a complex of nylon, CCl4, H2O and MMA is formed, was proposed.