Chemorheology of Irradiation-Cured Natural Rubber. I. Stress Relaxation Mechanisms for Various Curing Systems in Natural Rubber at High Temperature

<jats:title>Abstract</jats:title> <jats:p>1. There was no difference of stress relaxation, either in air or in nitrogen, between DCP cures (Sample 1) and irradiation cures (Sample 2). This suggests that these vulcanizates have the same physical and chemical structures. In air Samples 1 and 2 underwent random scission of only the main chain. 2. In the case of irradiation-TMTD cures (Samples 4 and 5), the stress decay was also based on oxidative scission of the main chain. The number of moles of main chain scission, qm(t), was independent of the ratio ρ (of Nc(0)) based on the carbon—carbon bonds to Nm(0) based on the mono- and disulfide links). However, qm(t) was larger than that of Sample 2. The oxidative scission of the main chain seemed to be accelerated by mono- and disulfide. It was found from comparison of Samples 4 and 5 that TMTD cures (Sample 3) underwent random scission on the main chain. The stress relaxation in nitrogen for Samples 3, 4, and 5 was due to thermal scission of the crosslink. 3. The stress relaxation, either in air or in nitrogen, of accelerated-sulfur-cures (Sample 6) and irradiation-sulfur cures (Samples 7 and 8) was expressed by the sum of two exponential terms. The stress relaxation in air of Samples 6, 7, and 8 could be explained by the interchange reaction of polysulfide links and the random scission on the main chain. The stress decay in nitrogen of these vulcanizates was based on both interchange of polysulfide links and thermal scission of crosslinks. The rate of the interchange reaction in air was very closely consistent with that in nitrogen. 4. The apparent activation energy of oxidative scission of the main chain was about 21 kcal/mol for Samples 2, 6, 7, and 8 and 27 kcal/mol for Samples 3, 4, and 5.</jats:p>