Kinetics of thiuram–accelerated sulfur vulcanization

On the basis of continuous measurements in a Vuremo curemeter at 145°C, kinetics of tetramethylthiuram disulfide (TMTD)-accelerated sulfur vulcanization of natural rubber has been investigated. It was found that the cure rates increase with increasing TMTD concentration, the sulfur content being kept constant, up to a TMTD:S weight ratio of 2:1. Beyond this value, the cure rates again decrease. This TMTD:S ratio corresponds to 3.8 gram atoms of sulfur per mole TMTD, and it is in good agreement with findings that in TMTD-accelerated sulfur vulcanization systems the peak value of zinc dimethyldithiocarbamate (ZnDMDC) formation reaches an endvalue when the stocks contain 4 gram atoms of sulfur per mole TMTD. These facts lead us to suppose that ZnDMDC is the actual accelerator in TMTD-accelerated sulfur systems. Support for this view derives from our experiments with model curing systems as well as from the generally known practical experience that dithiocarbamates are faster accelerators than thiuram disulfides. For the reasons described above and for the finding that the dependences of the ultimate extent of vulcanization (network chain density) on the concentration of TMTD in the absence and in the presence of elemental sulfur are analogous, the mechanism of thiuram-accelerated sulfur vulcanization is very probably similar to that of sulfur-free thiuram vulcanization.     

Effect of zinc oxide concentration on the course of thiuram-accelerated sulfur vulcanization

Tetramethylthiuram disulfide-accelerated sulfur vulcanization of natural rubber has been investigated. Continuous measurements in a Vuremo curemeter at 145°C were used to estimate the effects of zinc oxide concentration on the induction periods, on the first-order rate constants, and on the ultimate extents of crosslinking, on the extents of degradation reaction (reversion), and on the extents of relaxation of vulcanizates at the cure temperature. The concentration of zinc oxide has practically no influence on the rate of thiuram-accelerated sulfur cure. The values of the ultimate extents of crosslinking increase with increasing the zinc oxide content in the rubber compound up to a certain limit corresponding to the theoretical amount of zinc oxide which is necessary for the formation of zinc dimethyldithiocarbamate from tetramethylthiuram disulfide and zinc oxide during the vulcanization reaction. From the point of view of the reversion, however, this limit value of zinc oxide concentration is not sufficient. The relaxation measurements provide the same results. On the basis of these, for thiuram-accelerated sulfur vulcanizations, the optimum zinc oxide content in the rubber mix of 2.5 phr has been calculated. This value is in very good agreement with the optimum value of zinc oxide concentration found for both sulfenamides and thiazoles-accelerated sulfur cures.     

Effect of aerosil on the course of thiuram accelerated sulfur vulcanization

Tetramethylthiuram disulfide (TMTD)-accelerated sulfur vulcanization of natural rubber has been investigated at temperatures from 100°C to 145°C. Continuous measurements in a Vuremo curemeter were used to estimate the extent of crosslinking, which was plotted against cure time. The cure curves as well as their linearized forms (dependences of the logarithm of the extent of vulcanization on the cure time) clearly show that at lower cure temperatures the course of the vulcanization differs significantly from the first-order rate law. These digressions have been removed by the addition of a highly dispersed silica gel, Aerosil, which simultaneously speeds up the course of the vulcanization up to the value corresponding to the rate of zinc dimethyldithiocarbamate (ZnDMDC)-accelerated sulfur vulcanization. These results are in accordance with our recent theory supposing that ZnDMDC is the actual accelerator in TMTD-accelerated sulfur systems. In the presence of Aerosil, the formation of ZnDMDC from TMTD is catalyzed via dispersed silica gel. Support for this view derives from the temperature dependences of vulcanization reactions. The activation energies of TMTD-accelerated sulfur vulcanizations in the absence (31 kcal/mole) and in the presence of Aerosil (23.5 kcal/mole) correspond exactly to the values calculated from the rate constants of the thiuram decrease in TMTD-accelerated vulcanization (30 kcal/mole) and from the rate constants of crosslinking in the dithiocarbamate-accelerated sulfur vulcanization (23 kcal/mole), respectively.     

A DSC study of curative interactions. IV. The interaction of tetramethylthiuram disulfide with ZnO,sulfur, and stearic acid

The interaction of combinations of sulfur, tetramethylthiuram disulfide (TMTD), ZnO, and stearic acid were investigated by differential scanning calorimetry in the absence of rubber. TMTD decomposed partially to tetramethylthiuram monosulphide on liquefaction. Sulfur and TMTD reacted at vulcanization temperatures, and although the exact composition of all the products was not established, several features involving DSC and HPLC analysis were interpreted in terms of the formation of tetramethylthiuram polysulfides (TMTP). TMTD decomposed much faster to volatile products such as Me₂NH, CS₂, and CS when heated in the presence of stearic acid. Contrary to literature reports on the facile reaction of TMTD and ZnO to yield zinc perthiomercaptides (or zinc dimethyldithiocarbamate), the TMTD/ZnO reaction was found to be extremely sluggish under a variety of conditions. In the presence of sulfur, too, the TMTD/ZnO reaction was of negligible importance. It was inferred that several reactions occurred concurrently on heating a TMTD/stearic acid/ZnO system. These reactions were not observed for the sulfur/TMTD/stearic acid/ZnO mixture per se, but, instead, the stearic acid/ZnO reaction was very prominent. The formation of zinc stearate occurred at temperatures as low as 77°C in the quadruple system. TMTD and zinc stearate were virtually unreactive at vulcanization temperatures. None of the reactions involving ZnO could be attributed to the formation of a zinc perthiomercaptide, generally accepted to be a precursor in thiuram vulcanization.     

Kinetics of sulfur-free thiuram vulcanization

Sulfur-free thiuram vulcanization has been investigated at temperatures from 160° to 190°C over 0.5 to 600 min. Continuous measurements in a VUREMO curemeter were used to estimate the extent of crosslinking, which was plotted against cure time. Simultaneously the values of the network chain density were calculated from swelling measurements on the vulcanizates. The cure curves show clearly an induction period (t_i), then fast crosslinking, a partial degradation, a “long-time” crosslinking, and finally a slow, limited degradation. Apart from the induction period, the kinetic graphs are satisfactory represented by a rate equation assuming three independent first-order reactions: fast crosslinking, degradation, and slow crosslinking. The rate equation contains seven kinetic parameters. Over the temperature range studied, there is no difference between the values of activation energy for fast crosslinking, for degradation, for slow crosslinking, and for t. Due to the presence of thiourea, the values of the induction period, the rate constant, and the extent of slow crosslinking are decreased. Simultaneously the activation energies calculated from degradation and slow crosslinking are significantly increased. On the basis of the above results, the mechanism of the sulfur-free thiuram vulcanization, in which ionic and radical reactions take place, is discussed.     

Tetramethylthiuram disulfide and 2-mercaptobenzothiazole as binary accelerators in sulfur vulcanization. II. Exchange reactions between the accelerators and their zinc salts in the absence of rubber

Exchange reactions between tetramethylthiuram disulfide, 2-mercaptobenzothiazole, and sulfur in the presence of ZnO were studied by heating powdered mixes to vulcanization temperatures at a preprogrammed rate in a DSC. The reaction was stopped at points along the thermal curve and the mixture was analyzed. Sulfide exchange reactions between the accelerators leads to a mixed accelerator and dimethyldithiocarbamic acid that is trapped by ZnO to give the zinc accelerator complex bis(dimethyldithiocarbamato)zinc (II). Exchange also occurs between the accelerators and ligands on both the thiuram and benzothiazole zinc accelerator complexes. Zinc complexes containing ligands of both accelerators were synthesized. These showed little interaction on being heated with sulfur, but on dissolution yielded a spectrum of products similar to that obtained in the other system containing zinc. Reactions to account for changes in the spectrum of products on heating different mixes of these curatives to different temperatures are discussed. © 1995 John Wiley & Sons, Inc.     

Studies on cure synergism. I. Effect of safe zinc dithiocarbamates on NR vulcanization accelerated by thiazole-based accelerators

Investigations have been carried out on the effect of several zinc dithiocarbamates in the presence of thiazole-based accelerators in the vulcanization of natural rubber (NR), keeping in mind the possibility of introducing safe dithiocarbamates derived from safe amines. Mutual activity is observed in all the binary systems studied, the highest being observed in the zinc dibenzyldithiocarbamate-dibenzothiazyldisulfide (ZBEC–MBTS)-accelerated system. The effect of zinc diisopropyl dithiophosphate, reportedly a safe rubber additive, which is recognized as an age-resistant agent for NR, on cure has also been studied. The study reveals that thiuram disulfide and MBT are always formed from the reaction either between zinc dithiocarbamate (ZDC) and MBTS or between ZDC and N-cyclohexyl-2-benzothiazole sulfenamide (CBS). It has been conclusively proved that 2-mercaptobenzothiazole (MBT) generated from MBTS or CBS reacts with ZDC and produces tetramethyl thinram disulfide (TMTD). The observed mutual activity has been discussed based on the cure and physical data and explained through the results based on HPLC and a reaction mechanism. © 1994 John Wiley & Sons, Inc.     

A comparison of the tetramethylthiuram disulphide accelerated sulfur vulcanization of polybutadiene and polyisoprene

A detailed study of the vulcanization of polybutadiene with various combinations of sulphur, tetramethylthiuram disuphide, ZnO, stearic acid, and zinc dimethyldithiocarbamate is reported. Vulcanization was conducted by heating samples at 2.5°C/min in a differential scanning calorimeter. The reaction was stopped at various points along the vulcanization exotherm, the soluble reaction products and residual curatives were extracted and analyzed, and the crosslink density and percentage polysulphidic crosslinks were determined. The overall reaction mechanism was found to be similar to that for polyisoprene, but the reaction, once initiated, was faster than in polyisoprene, the crosslink density was higher, and the percentage polysulphidic crosslinks was lower. These differences are discussed. © 1993 John Wiley & Sons, Inc.     

Temperature dependence of mooney scorch time of rubber compounds

A study of the temperature dependence of Mooney scorch time was carried out by using two grades of natural rubber, Hevea Brasiliensis(SMR L and SMR 10), and on synthetic rubber, styrene—butadiene rubber (SBR), in the temperature range of 100–180°C. Results show that the scorch time for SBR system is greater than that of the other grades of natural rubber. This is attributed to the lower degree of unsaturation in SBR. Effects of 2-mercaptobenzothiazole (MBT) and other types of accelerators on the scorch properties were also investigated and discussed. One black-filled compound was used to study the dependence of carbon black on the scorch property, and data indicate that the effect is more evident for temperature lower than 100°C.     

Dimethylammonium dimethyldithiocarbamate‐accelerated sulfur vulcanization. II. Vulcanization of rubbers and model compound 2,3‐dimethyl‐2‐butene

Rubber and model compound 2,3‐dimethyl‐2‐butene were vulcanized for various times with dimethylammonium dimethyldithiocarbamate [(dma)dmtc]‐accelerated sulfur formulations in the absence of ZnO. Model compound systems were analyzed by HPLC, and no reaction intermediates containing pendent groups were found. Crosslinked sulfides, characterized by ¹H‐NMR, were found to be essentially bis(alkenyl). Residual curatives were extracted from rubber compounds vulcanized for various times and analyzed by HPLC. Compounds, cured to various crosslink densities, were found to crystallize readily in a density column at subambient temperatures. This supports evidence from model compound systems that pendent groups are largely absent from vulcanizates. It is suggested that a reaction mechanism, similar to that applicable to zinc dimethyldithiocarbamate‐accelerated sulfur vulcanization, may be applicable with (dma)dmtc accelerated formulations. Very limited crosslinking occurred on heating compounds under vacuum, and this can be attributed largely to the rapid loss of (dma)dmtc from rubber at elevated temperatures. However, the slower rate of crystallization on cooling of the gels, compared to the rate in press‐cured vulcanizates of similar crosslink density, was interpreted as evidence that some pendent groups did form during heating with (dma)dmtc/sulfur. Crosslinking of such pendent groups may be inhibited by the loss of (dma)dmtc, that, like zinc dimethyldithiocarbamate, may catalyze their crosslinking, and/or to the loss under vacuum of dimethyldithiocarbamic acid that would form thiol pendent groups that would rapidly crosslink with thiuram pendent groups. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 3074–3083, 2001     

Effect of temperature on the course of thiuram-accelerated sulfur vulcanization

Tetramethylthiuram disulfide-accelerated sulfur vulcanization of styrene-butadiene rubber has been investigated at temperatures from 100°C to 170°C over 0.5 to 600 min. Continuous measurements in a Vuremo curemeter were used to estimate the extent of crosslinking, which was plotted against cure time. Apart from the induction period (t_i), the kinetic graphs are satisfactory represented by a rate equation assuming three independent first-order reactions: fast crosslinking, degradation, and slow crosslinking. The rate equation contains seven kinetic parameters. Over the temperature range studied, there is no difference between the values of activation energy for t_i^?1, for fast crosslinking, and for degradation. The activation energy of slow crosslinking only is significantly greater. Due to the presence of Aerosil, the reciprocal values of the induction periods and the values of the ultimate extents of fast crosslinking are increased, and the values of the rate constants of degradation and slow crosslinking are decreased. Simultaneously, the activation energy of slow crosslinking is also significantly decreased. On the basis of these results, the proposed theory of tetramethylthiuram disulfideaccelerated sulfur vulcanization supposing that zinc dimethyldithiocarbamate is the actual accelerator in this type of curing system is discussed.     

Structural characterization of vulcanizates. Part VI. The 2-mercaptobenzothiazole-accelerated natural rubber–sulfur system

The crosslinking efficiency of sulfur in the vulcanization of natural rubber in the presence of 2-mercaptobenzothiazole, zinc oxide, and lauric acid has been determined as a function of cure time, cure temperature, and lauric acid concentration. With a low concentration of lauric acid structurally complex networks are formed, which contain 11–19 combined sulfur atoms per chemical crosslink present. The complexity increases with time of vulcanization. With a high lauric acid concentration much simpler networks are formed, which become progressively more simple as reaction proceeds (6 network-combined sulfur atoms per chemical crosslink, decreasing to 2.4 with time). Increasing the cure temperature from 100 to 140°C. reduces the efficiency of crosslinking in both cases. The changes in efficiency are attributed to the influences of the reaction variables (in particular, the concentration of rubber-soluble complexes of the zinc laurate with zinc benzothiazolyl mercaptide) on the structure and subsequent reactions of initially formed polysulfidic crosslinks.     

Dimethylammonium dimethyldithiocarbamate‐accelerated sulfur vulcanization. I. Thermal stability and reactions with curatives

To investigate its thermal stability and reactivity towards other accelerators dimethylammonium dimethyldithiocarbamate ((dma)dmtc) was heated at programmed heating rates in sealed and open pans in a differential scanning calorimeter and on a thermobalance. (Dma)dmtc was heated on its own, in rubber compounds and in mixes with tetramethylthiuram disulfide, zinc dimethyldithiocarbamate, and ZnO. In open systems (dma)dmtc readily sublimes at temperatures well below its melting point, and it is almost as rapidly lost when compounded on its own with rubber. No decomposition is observed at vulcanization temperatures and (dma)dmtc is unreactive towards tetramethylthiuram disulfide and zinc dimethyldithiocarbamate. Moisture does not promote its decomposition. Reaction with ZnO to give zinc dimethyldithiocarbamate is restricted to the surface of ZnO particles. (Dma)dmtc is soluble in water in which it dissociates. It must be concluded that when its is included in formulations, (dma)dmtc, per se, would act as a vulcanization accelerator; it does not decompose to dimethyldithiocarbamic acid and dimethylamine, both of which are known accelerators. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 3067–3073, 2001     

Mooney scorch time of epoxidized natural rubber

The scorch property of accelerated sulfur vulcanization of three grades of expoxidized natural rubber (viz. ENR 10, ENR 25, and ENR 50) was studied by using Mooney Shearing Disk Viscometer in the temperature range of 100–180°C. Effects of accelerator types, concentration of accelerator, and carbon black on ENR 10 were also determined. Results obtained indicate a similar scorch behavior as that reported earlier for SMR L. However, some differences in the magnitude of scorch times in the temperature and concentration studies are observed between ENR and SMR L. These differences are attributed to the activation of a double bond by the adjacent epoxide group in ENR, the effect being more significant for a higher degree of epoxidation of natural rubber. In the case of ENR 50, differential scanning calorimetry measurement suggests that additional crosslink occurs via a ring-opening reaction at about 155°C. Based on first-order reaction kinetics, the apparent activation energy of vulcanization for the rubbers studied is estimated and discussed.     

Mooney scorch time and cure index of epoxidized natural rubber in presence of sodium carbonate

The effect of sodium carbonate on the Mooney scorch time and cure index of epoxidized natural rubber (ENR 50) was studied with concentrations of 0–2 phr and 100–160°C temperatures. A conventional vulcanization system based on an ASTM formulation was used throughout the investigation on the gum and carbon black filled rubber compound. The results indicated that the scorch time and cure index for the gum and filled compounds increased to a maximum value at 0.15 phr of sodium carbonate, and further loading of sodium carbonate caused it to decrease. This observation was attributed to the neutralization of the residual acid in ENR 50 in the initial stage, thus reducing the formation of ether crosslinks via an acid‐catalyzed ring‐opening reaction with the epoxide group in ENR 50. However, as the sodium carbonate was increased beyond 0.15 phr, the excess sodium carbonate enhanced the vulcanization rate as shown by the drop of the scorch time and cure index. The peak maximum was more evident at lower temperature and its peak height decreased with increasing temperature, suggesting that the neutralization effect by sodium carbonate was overshadowed by the faster cure rate resulting from the availability of thermal energy to overcome the activation energy of vulcanization as the temperature was elevated. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1352–1355, 2001     

Efficiency of metal activators of accelerated sulfur vulcanization

The effects of copper, mercury, nickel, zinc, cadmium, indium, magnesium, and calcium stearates on the course of N-cyclohexyl-2-benzthiazylsulphenamide-accelerated sulfur vulcanization of natural rubber have been investigated on the basis of curemeter measurements at 145°C. The differences in the efficiencies of these metal activators of accelerated sulfur vulcanization have been discussed from the points of view of the electron configurations of the metals and their affinities to sulfur. We attempted to determine why zinc oxide is generally accepted as the best metal vulcanization activator. © 1993 John Wiley & Sons, Inc.     

Cure characteristics of unaccelerated sulfur vulcanization of epoxidized natural rubber

The curing characteristics of unaccelerated sulfur vulcanization of ENR 25 and ENR 50 were studied in the temperature range from 100–180°C. The range of sulfur loading was from 1.5 to 6.5 phr. The scorch time was determined by Mooney Shearing Disk Viscometer whereas the initial cure rate, maximum torque, and reversion properties were obtained from the Moving Die Rheometer (MDR 2000). Results shows that ENR 25 gives a longer scorch time than ENR 50, an observation similar to that in an accelerated system reported earlier. For temperature < 120°C, scorch time depends exponentially on sulfur loading for both rubbers. However, this dependence diminishes as temperature is increased. This observation is attributed to the availability of activated sulfur molecules for vulcanization. The initial cure rate and maximum torque increases with increasing sulfur loading. ENR 50, however, exhibits higher value than ENR 25, suggesting faster cure in the former. For a fixed sulfur loading, reversion is a time and temperature-dependent phenomenon. It decreases with increasing sulfur loading because of the increase of cross-linking density for both rubbers stuided. © 1996 John Wiley & Sons, Inc.     

Sulfur vulcanization of polyisoprene accelerated by benzothiazole derivatives. II. Reaction of 2-mercaptobenzothiazole and its zinc salt with sulfur and ZnO in polyisoprene

Compounds of polyisoprene with sulfur and bis(2-mercaptobenzothiazole)zinc(II) (Zn(mbt)₂) or ZnO and 2-mercaptobenzothiazole (MBT) were vulcanized by heating in a differential scanning calorimeter. The reaction was stopped at points along the thermogram and the product analyzed. ZnO and MBT readily react, the reaction going to completion during compounding. The presence of Zn(mbt)₂ delays the onset of crosslinking compared to compounds without zinc. It is suggested that the induction period prior to crosslinking is occasioned by the inactivity of Zn(mbt)₂, which must breakdown to MBT before it can participate in the vulcanization process. Such decomposition results from attack by anions generated when polysulfidic crosslinks, formed in the unaccelerated sulfur that occurs in the early stages of crosslinking, undergo scission. The effect of MBT, not bound to zinc, on the mechanism of the reaction is discussed. © 1995 John Wiley & Sons, Inc.     

Effects of silane coupling agents on the vulcanization characteristics of natural rubber

The vulcanization characteristics of silica‐filled natural rubber (NR) were studied in the presence of silane coupling agents, 3‐octanoylthio‐1‐propyltriethoxysilane (NXT) and bis [(3‐triethoxysilylpropyl) tetra sulfide] (TESPT, or Si‐69). The scorch time, cure rate index, and the rate constant of NR were measured using an Oscillating Disk Rheometer in the temperature range of 140–170°C. The scorch time of NR decreases with increasing TESPT and NXT concentrations, and the scorch time of NR compound with NXT is longer than that with TESPT. The apparent activation energies of vulcanization for the compounds with NXT and TESPT both decrease with increasing silane concentration. The apparent activation energy of vulcanization of NR compound with NXT is lower than that with TESPT at various concentrations. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1511–1518, 2004     

Evidence of ionic components in vulcanization mixtures by means of electric current measurements: Investigations with natural rubber/sulfur/zinc bis(dimethyldithiocarbamate) and comparison mixtures

Continuous low‐level current (CLLC) measurements for detecting ionic species in the course of vulcanization reactions were applied to investigate the vulcanization of a mixture of natural rubber (NR), sulfur (S), and zinc bis(dimethyldithiocarbamate) (ZnDMTC). A dc voltage was applied to the reaction mixture in a special vulcanization mold and the current (e.g., in the range of 10⁻⁹ A) was measured. Temperature‐dependent current maxima were found after reaction times t_max. The simplest explanation is that transitory ionic species occur during vulcanization. An activation energy (E_a ) = 116.4 kJ/mol, similar to that obtained in previous chemical investigations, was determined from the decrease of t_max with increasing temperature. The maxima corresponded to reaction times where a strong increase of polymer crosslinking was observed, as measured using vulcametry. For comparison, dc measurements were carried out with the corresponding mixture without elemental sulfur (NR/ZnDMTC) and mixtures containing zinc stearate (ZnST) instead of zinc bis(dimethyldithiocarbamate) (NR/S/ZnST and NR/ZnST). © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2206–2212, 2000