Structural Characterization of Vulcan-Izates. XII. Efficient Vulcanization Using a Sulfenamide-Thiuram Disulfide Accelerator System

1972 ◽  
Vol 45 (5) ◽  
pp. 1366-1371 ◽  
Author(s):  
D. S. Campbell

Abstract Vulcanizates obtained from the sulfur vulcanization of natural rubber using a combination of the accelerators N-cyclohexyl-2-benzothiazole sulfenamide (CBS) and tetramethylthiuram disulfide (TMTD) have been analyzed in terms of the numbers of poly-, di-, and monosulfide crosslinks, network-bound accelerator residues, and cyclic sulfide chain modifications as a function of cure time. The vulcanization system produced mainly monosulfide crosslinks at optimum cure, although there were differences in detail between this mixed system and a previously reported efficient sulfur vulcanization (EV) system using a high ratio of CBS to sulfur.

1970 ◽  
Vol 43 (2) ◽  
pp. 210-221 ◽  
Author(s):  
D. S. Campbell

Abstract The thiol-disulfide exchange reaction is shown to be applicable to cleavage of disulfide crosslinks in accelerated sulfur vulcanizates of natural rubber. The reaction, in conjunction with the previously reported selective cleavage of polysulfide crosslinks, is used to determine the distribution of crosslink types for several accelerated sulfur vulcanization systems as a function of cure time. Discrepancies between the results and published results obtained using the reagent sodium di-n-butyl phosphite for disulfide crosslink cleavage are discussed.


1983 ◽  
Vol 56 (4) ◽  
pp. 827-837 ◽  
Author(s):  
D. Pal ◽  
B. Adhikari ◽  
D. K. Basu ◽  
A. K. Chaudhuri

Abstract N-cyclopentamethylenethiocarbamyl-N′-cyclopentamethylenesulfenamide (CPTCS) and dibenzothiazyldisulfide (MBTS), as binary accelerators in a mixture have been found to provide significant mutual enhanced activity with regard to modulus, tensile strength, hardness, and elongation at break in the vulcanization of NR gum stocks. The synergistic activity of the CPTCS-MBTS system is very much dependent upon the accelerator ratios, concentration of sulfur and accelerator, as well as the temperature of vulcanization. Investigations carried out with the Monsanto rheometer also corroborate the above results. It is suggested that the synergism arises out of the interaction between CPTCS and MBTS which produces intermediate accelerators. N,N-Diethylthiocarbamyl-N′-cyclohexylsulfenamide (DETCS) in conjunction with MBTS, produces similar results in the vulcanization of NR. Structural characterization of the vulcanizates obtained at 140 and 160°C reveals that predominantly monosulfidic linkages are obtained with CPTCS or DETCS and MBTS combinations. The intermediate combinations, at near equimolar concentration of the two accelerators, exhibit maximum crosslink density. An attempt has been made to correlate physical properties with crosslink density as well as various types of crosslinks.


2011 ◽  
Vol 84 (1) ◽  
pp. 88-100 ◽  
Author(s):  
R. Reshmy ◽  
R. Nirmal ◽  
S. Prasanthkumar ◽  
K. Kurien Thomas ◽  
Molice Thomas ◽  
...  

Abstract The vulcanization of natural rubber and a blend of natural rubber and reclaimed rubber by using binary accelerator systems containing a novel series of benzothiazoloylthiazole as secondary accelerator (SA) has been studied. These secondary accelerators were synthesized by a green chemical method under solvent-free conditions, by the irradiation of microwaves (180 W). The synergistic effect of the SA with N-Cyclohexyl-2-benzothiazolsulfenamide as primary accelerator was studied at 150 °C. These binary systems were effective in reducing the cure time and improving the rheometric and mechanical properties. These SAs were found to be effective in reducing the cure time with a minimal amount of 0.5 phr, but commercially available SAs such as thioureas and tetramethylthiuram disulfide were reported to show reduction in cure time only by increasing the amount of SA. Mechanical properties such as hardness, abrasion loss, tensile strength, percentage strain at break, and modulus at different elongations 100, 200, and 300% were evaluated and found to be immensely improved. The improved mechanical properties were also shown to be at par with crosslink densities (1/2Mc) of different mixes.


Author(s):  
IHK Samarasinghe ◽  
S Walpalage ◽  
DG Edirisinghe ◽  
SM Egodage

An outstanding interest on elimination of nitrosamine generation in traditional sulfur vulcanization systems has led to introduce nitrosamine safe accelerator/s to produce safe natural rubber (NR) vulcanizates. It is an effective way to prevent formation of carcinogenic N-nitroso compounds during manufacture of rubber products. In the present study, behavior of nitrosamine safe binary accelerator system consisting of diisopropyl xanthogen polysulfide (DIXP) with commonly used non-regulated accelerator N-tert-butyl-2-benzothiazole sulfenamide (TBBS) was investigated in efficient sulfur vulcanization of NR. Cure characteristics, physico-mechanical properties and crosslink density of vulcanizates prepared with different combinations of the accelerator system were evaluated and compared with those of individual accelerators. The study reveals that moduli and strength properties of the vulcanizate prepared with DIXP accelerator are inferior to those of the vulcanizate prepared with TBBS accelerator. Nevertheless, optimum cure time of the DIXP compounds is lower in comparison to TBBS compounds. Moreover, progressive replacement of DIXP with TBBS in the accelerator system showed a synergistic effect in regard to cure characteristics and physico-mechanical properties.


1970 ◽  
Vol 43 (6) ◽  
pp. 1294-1310 ◽  
Author(s):  
S. P. Manik ◽  
S. Banerjee

Abstract The salient features of both non-elemental sulfur vulcanization by TMTD and elemental sulfur vulcanization promoted by TMTD both in presence and absence of ZnO and stearic acid have been studied. TMTD increases the rate of DCP decomposition and lowers the crosslinking maxima due to DCP depending on its concentration. However, with higher amounts of TMTD the initial rate of crosslinking is increased with the increased amount of TMTD, while crosslinking maxima are still lowered due to reversion. ZnO or ZnO-stearic acid, however, seems to alter the entire course of the reaction. Both the crosslink formation and TMTD decomposition are much higher in presence of ZnO or ZnO-stearic acid, but stearic acid seems to have no effect. The reaction mechanisms for TMTD accelerated sulfuration in absence and presence of ZnO have also been studied.


2012 ◽  
Vol 190 ◽  
pp. 24-28 ◽  
Author(s):  
Cristina Artini ◽  
Giorgio A. Costa ◽  
Marcella Pani ◽  
Andrea Lausi ◽  
Jasper Plaisier

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