Structural characterization of vulcanizates. Part VII. The N-cyclohexylbenzothiazole-2-sulfenamide-accelerated natural rubber–sulfur system

The crosslinking efficiency of sulfur in the vulcanization system comprising (in parts by weight) natural rubber (100), sulfur (1.5), N-cyclohexylbenzothiazole-2-sulfenamide (2.37), zinc oxide (5), and lauric acid (1–10) is relatively insensitive to the lauric acid concentration and to the temperature of vulcanization (between 100 and 140°C.). The networks formed contain initially 8–11 combined sulfur atoms per chemical crosslink present, but this number falls progressively to about 4 as the reaction proceeds. The results are consistent with the intermediate formation of a rubber-soluble complex of cyclohexylamine with zinc benzothiazolyl mercaptide. This complex is believed to be responsible also for the further slow crosslinking which the vulcanizates undergo on standing at room temperature.     

A comparison of tetraethylthiuram and tetramethylthiuram disulfide vulcanization. II. Reactions in rubber

The reactions of tetraethylthiuram disulfide (TETD) with polyisoprene were investigated under vulcanization conditions. Samples of polyisoprene compounded with various combinations of TETD, sulfur, and ZnO were heated in a differential scanning calorimeter to various degrees of vulcanization. The crosslink density of the compounds was determined by swelling, and the extractable residual curatives and reaction products were analyzed with high‐performance liquid chromatography. TETD caused crosslinking to occur in the absence of added sulfur, as did tetramethylthiuram disulfide (TMTD), both sulfur donors. In the presence of sulfur, the formation of TETD polysulfides occurred immediately before the crosslinking reaction started. The TETD polysulfides were the initial crosslinking agents. The ready reaction between TETD and zinc oxide to form zinc diethyldithiocarbamic acid resulted in considerably higher crosslink densities. This greater reactivity between TETD and zinc oxide, compared with that between TMTD and zinc oxide, did not lead to any noticeable differences in the vulcanizate. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1119–1127, 2002     

Kinetics of accelerated vulcanization. Sulfur vulcanization accelerated with 2-mercaptobenzothiazole and its zinc salt in presence of zinc oxide and zinc oxide and stearic acid

Sulfur vulcanization of natural rubber (NR) and styrene-butadiene rubber (SBR) accelerated with 2-mercaptobenzothiazole and zinc oxide with or without stearic acid has been studied and the results compared with those obtained by replacing the thiazole with its zinc salt. The order of the rate of vulcanization as measured from free sulfur decrease or crosslink formation is observed to be unity with respect to time and less than one with respect to accelerator concentration. In absence of stearic acid, the zinc salt is much less efficient than the thiazole in promoting vulcanization, and the efficiency of the latter shows a noticeable improvement over what is attained in absence of zinc oxide. Addition of stearic acid not only raises the efficiency of both the systems to the same level but also leads to a faster rate of vulcanization, a much higher degree of crosslinking, avoidance of reversion, and production of vulcanizates with considerably improved mechanical properties. The formation of zinc sulfide also reveals interesting variation. Attempts have been made to interprete these results in terms of complex formation between zinc salt of thiazole and zinc stearate.     

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.     

Structural characterization of vulcanizates. Part VIII. The N-cyclohexylbenzothiazole-2-sulfenamide-accelerated sulfur vulcanization of natural rubber at 140–180°C. and of synthetic cis-1,4-polyisoprene at 140°C

Vulcanization of natural rubber at 140°C. with a CBS-accelerated sulfur system of conventional type gives rise to a structurally complex network in which the number of sulfur atoms combined per chemical crosslink present increases from 12 to 21 with increasing reaction time. The complexity of the network increases with increasing temperature of vulcanization. Crosslinking of a purified synthetic cis-1,4-polyisoprene proceeds more slowly and yields a slightly more complex network. Despite this overall similarity the natural rubber vulcanizates exhibit considerably higher tensile strengths.     

Influence of zinc oxide during different stages of sulfur vulcanization. Elucidated by model compound studies

The addition of zinc oxide (ZnO) as an activator for the sulfur vulcanization of rubbers enhances the vulcanization efficiency and vulcanizate properties and reduces the vulcanization time. The first part of this article deals with the reduction and optimization of the amount of ZnO. Two different rubbers, solution‐styrene‐butadiene rubber and ethylene–propylene–diene rubber, have been selected for this study. The results demonstrate that the curing and physical properties can be retained when the level of ZnO (Red Seal) is reduced to 1 or 2 phr, respectively. Of particular interest is nano‐ZnO, characterized by a nanoscale particle distribution. The cure characteristics indicate that with nano‐ZnO, a reduction of zinc by a factor of 10 can be obtained. In the second part, model compound vulcanization is introduced to investigate the effects of ZnO during the different stages of vulcanization. Experiments are described with two models, squalene and 2,3‐dimethyl‐2‐butene, both with benzothiazolesulfenamide‐accelerated vulcanization systems. The results demonstrate the influence of ZnO during the different stages of the vulcanization. With ZnO present, a marked decrease can be observed in the sulfur concentration during an early stage of vulcanization, along with a slight delay in the disappearance of the crosslink precursor. The crosslinked product distribution is influenced as well. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1388–1404, 2005     

Sulfur vulcanization of polyisoprene accelerated by benzothiazole derivatives. I. Comparison of sulfur and 2-mercaptobenzothiazole accelerated reactions

Polyisoprene compounds with sulfur and with sulfur and 2-mercaptobenzothiazole (MBT) were vulcanized by heating in a differential scanning calorimeter (DSC) at a programmed rate. The reaction was stopped at various temperatures along the thermogram and the product analyzed by determining the crosslink density and crosslink type, and by determining the amount of extractable curatives and soluble reaction products by high-performance liquid chromatography. DSC cure curves and plots of crosslink density and extractable sulfur vs. temperature for the unaccelerated and MBT accelerated compounds can be made to coincide by shifting them along the temperature axis. It is suggested that MBT accelerated sulfur vulcanization occurs by the same mechanism as unaccelerated sulfur vulcanization, with SH⁺ ions from MBT adding across the carbon–carbon double bond, thus increasing the rate at which the reaction is initiated. © 1995 John Wiley & Sons, Inc.     

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.     

Sulfur vulcanization of polyisoprene accelerated by benzothiazole derivatives. III. The reaction of 2-bisbenzothiazole-2,2′-disulfide with sulfur and ZnO in polyisoprene

The sulfur vulcanization of polyisoprene accelerated by 2-bisbenzothiazole-2,2′-disulfide (MBTS) was investigated. Rubber compounds were heated in a DSC and removed at various temperatures along the DSC thermal curve. The rubber vulcanizate was analyzed for crosslink density and for residual reactants and extractable reaction products. MBTS reacts readily with sulfur, and the polysulfidic accelerator complexes react with the rubber chain to form pendent groups. Crosslinking results from hydrogen abstraction, by the benzothiazole pendent group, from a neighboring chain. 2-Mercaptobenzothiazole, a product of crosslinking, also acts as an accelerator in the later stages of the reaction. MBTS has been shown not to react with ZnO and the higher crosslink densities obtained when ZnO is present are attributed to ZnO aiding the abstraction of the benzothiazole pendent group to give zinc mercaptobenzothiazole. A mechanism for the MBTS acceleration of sulfur vulcanization is proposed. © 1996 John Wiley & Sons, Inc.     

Vulcanization of chlorobutyl rubber. III. Reaction mechanisms in compounds containing combinations of zinc dimethyldithiocarbamate,tetramethylthiuram disulfide,sulfur, and ZnO

Poly(isoprene‐co‐isobutylene) (IIR or butyl) and chlorinated poly(isoprene‐co‐isobutylene) (CIIR or chlorobutyl) compounds containing combinations of zinc dimethyldithiocarbamate [Zn₂(dmtc)₄], tetramethylthiuram disulfide (TMTD), sulfur, and ZnO were vulcanized at 150°C, the reaction was stopped at various points, crosslink densities were determined by swelling, and the concentrations of residual curatives and extractable reaction intermediates and products were determined by high‐performance liquid chromatography and atomic absorption (ZnCl₂). In compounds that did not contain zinc, CIIR crosslinked more slowly than IIR and crosslinking could be explained by the same mechanism as applies to the vulcanization to highly unsaturated rubbers like polyisoprene. In zinc containing compounds, CIIR crosslinked faster because of dehydrohalogenation reactions that led to carbon–carbon crosslinks. As found with ZnO/ZnCl₂ formulations, both ZnCl₂ and conjugated diene butyl are essential precursors to crosslink formation. Zn₂(dmtc)₄ can trap HCl, thus preventing reversion and may also initiate dehydrohalogenation. When the equilibrium crosslink density is reached, 50% of the chlorine originally present in the rubber is extractable as ZnCl₂ and the remainder as dimethylthiocarbamic acid chloride. A mechanism to account for dehydrochlorination and crosslinking in the presence of Zn₂(dmtc)₄ is presented. In compounds with sulfur, crosslinking occurs via accelerated sulfur vulcanization and chlorine abstraction, leading to higher crosslink densities than is achieved with either curative system on its own. Carbon–carbon crosslinks predominate, the slower, accelerated sulfur reaction, making a lesser contribution to the overall reaction. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1309–1316, 2001     

The role of thiol intermediates in 2‐mercaptobenzothiazole accelerated sulfur vulcanization of rubber model compounds

The model compound, 2,3‐dimethyl‐2‐butene (TME), was vulcanized using 2‐mercaptobenzothiazole (MBT) and sulfur. MBT was not consumed during the vulcanization reaction. The resultant crosslink products were bis(alkenyl) in nature. 2,3‐Dimethyl‐2‐buten‐1‐thiol (TME‐SH) was identified as being present in the vulcanization mixture by a postcolumn derivatization technique. The appearance of thiol was coincident with crosslinking. Polysulfanes (H₂S_n) were formed on crosslinking. Studies of the reaction of TME‐SH and sulfur indicated a rapid reaction to form crosslink products and polysulfanes. No monosulfidic crosslink species were formed in these reactions. Closer investigation revealed the presence of small quantities of what appeared to be highly reactive polysulfidic thiols. This is the first time that such species have been identified in vulcanization systems. Consequently, MBT‐accelerated vulcanization of TME is proposed to occur via the reaction of MBT and S₈ to form polysulfidic MBT, which then reacts with TME to form polysulfidic thiols. These thiols then rapidly react via a metathesis reaction pathway to provide crosslink products and polysulfanes. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 47–54, 2003     

Study of curative interactions in cis-1,4-polyisoprene. XII. The cis-1,4-polyisoprene–sulfur–tetramethylthiuram disulphide–ZnO–stearic acid vulcanization system

Several aspects on the mechanism of vulcanization in the synthetic cis-1,4-polyisoprene (IR)-sulfur-tetramethylthiuram disulphide (TMTD)–ZnO system were harmonized. The differential scanning calorimetry (DSC) thermograms showed that the vulcanization processes became better resolved on increasing the curative loading in the compound. Two major crosslinking reactions occurred consecutively in the IR (100)–sulfur (9.46)–TMTD (8.86)–ZnO (3.00) mixture, viz the IR–sulfur–TMTD–ZnO and IR–sulfur–zinc dimethyldithiocarbamate (ZDMC) (or IR–sulfur–ZDMC–ZnO) reactions. In the first process poly-and disulfidic pendent groups RS_xSX (R = polyisoprenyl, X = Me₂NC (S), x ≥ 1) formed via the IR–XSS_xSX reaction, and in the second via the IR–XSS_xZnSSX reaction. Thermogravimetric analysis (TGA) and high-pressure liquid chromatography (HPLC) data showed that dimethyldithiocarbamic acid liberated during the IR–sulfur–TMTD–ZnO reaction was trapped by ZnO to yield ZDMC. Hence ZDMC was a product, and not precursor, of this crosslinking process. A comparison of reactions in IR–sulfur–TMTD–ZnO and poly(ethylene-co-propylene)–sulfur–TMTD–ZnO mixtures showed that the participation of IR molecules was essential for ZDMC formation. The ZDMC concentration remained constant at ～ 38.4 mol % during the later stages of cure, showing that it did not participate in the desulfuration reactions of polysulfidic links. In the presence of stearic acid the stearic acid–ZnO reaction occurred at 87°C as was manifested by an intense crystallization peak of zinc stearate. The vulcanization processes were the same both in the presence and absence of stearic acid.     

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.     

N,N′‐Pentamethylenethiuram disulfide and N,N′‐pentamethylenethiuram hexasulfide accelerated sulfur vulcanization. III. Vulcanization of polyisoprene and 2,3‐dimethyl‐2‐butene in the absence of ZnO

Polyisoprene and model compound, 2,3‐dimethyl‐2‐butene, were vulcanized with N,N′‐dipentamethylenethiuram disulfide (CPTD), CPTD/sulfur and N,N′‐dipentamethylenethiuram hexasulfide (CPTP6) in the absence of ZnO and residual extractable curatives and reaction intermediates analyzed by HPLC at various stages of the reaction. Accelerator polysulfides, required for the formation of accelerator‐terminated polysulfidic pendent groups, form rapidly, or are present from the outset in the case of CPTP6. Model compounds confirm the formation of thiuram‐terminated polysulfidic pendent groups as intermediates in the vulcanization process. Removal of pentamethylenedithiocarbamic acid (Hpmtc) from the system during heating delays the onset of vulcanization and leads to very low crosslink densities. Rubbers heated under vacuum can subsequently be crosslinked by the addition of zinc stearate, pointing to the presence in the compound of thiuram‐terminated pendent groups. However, such pendent groups do not readily crosslink on their own, and hydrogen‐terminated polysulfidic pendent groups, formed by the reaction of sulfurated Hpmtc with the polymer, are suggested to be involved in the crosslink formation. N,N′‐Pentamethylenethiurea forms in the vulcanizate, but is not as product of crosslinking reactions, rather of CPTD degradation. The data are discussed with respect to mechanisms proposed in the literature for crosslinking, and it is concluded that the data support recently formulated mechanisms in which crosslinking involves reaction between thiuram and thiol‐terminated pendent groups, with Hmptc playing and essential role in the overall process. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1100–1111, 2000     

Structural characterization of vulcanizates part X. Thiol-disulfide interchange for cleaving disulfide crosslinks in natural rubber vulcanizates

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.     

Influence of prolonging vulcanization on the structure and properties of hard rubber

This research on vulcanization illuminates the structure–property relationship of hard rubber with prolonging vulcanization. At the early stage of curing, polysulfur reacts with styrene–butadiene rubber (SBR) macromolecules to form chemical crosslink, as evidenced by the significant increase of modulus during vulcanization. The chemical crosslink is followed by a large amount of interchain attraction, which is due to the modification of SBR macromolecules by combined sulfur. The combined sulfur is formed by the reaction of sulfur atom with SBR backbone, which improves the polarity of SBR macromolecules since sulfur is polar. The influences of chemical crosslink and interchain attraction on the mechanical properties, thermal properties, dynamic mechanical properties, and fracture morphology were analyzed. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

High temperature vulcanization of elastomers: 3. Network structure of efficiently vulcanized natural rubber mixes

The effect of vulcanization temperature (140–200°C) and time on the structures of pure gum natural rubber vulcanizates with two different N-cyclohexyl-2-benzothiazylsulphenamide (CBS): sulphur ratios (A, 3·5:1·5; B, 6·0:0·4 CBS/S) has been determined. Analyses of vulcanizates were carried out as reported in Part 2. Results show that both mixes are efficient in crosslinking, resulting in mainly monosulphidic crosslinks and relatively few modifications of the rubber chains. Raising the cure temperature from 140°C reduces the density of chemical crosslinks, particularly those of monosulphidic crosslinks, obtainable in the vulcanizates. This decrease in crosslink density has been shown to be irreversible with respect to cure temperature. The formation of intramolecular sulphidic groups and zinc sulphide increases with rising cure temperature, but this increase is small compared with that reported for the conventional CBS-accelerated system. The main difference between mixes A and B is that mix A yields a higher level of crosslinks and a major proportion of cyclic sulphides as main-chain modification. Negligible chain scission occurs during vulcanization at 140–200°C. These network results are interpreted mechanistically, and essential network features for obtaining good physical properties in high temperature vulcanizates are deduced.     

High temperature vulcanization of elastomers: 2. Network structures in conventional sulphenamide-sulphur natural rubber vulcanizates

A natural rubber (NR) gum mix with a conventional N-cyclohexyl-2-benzothiazylsulphenamide (CBS) accelerated sulphur system (0.5:2.5 CBS/S) was vulcanized at temperatures from 140°C to 200°C. The influence of cure temperature on (a) the chemical crosslink density, (b) the distribution of crosslink types, (c) the extent of sulphidic main-chain modifications, and (d) the zinc sulphide formation was investigated. Results show that elevated cure temperatures produce a network with a lower crosslink density, in particular a lower polysulphidic crosslink density. The formation of intramolecular sulphidic groups and zinc sulphide increases with increasing temperatures. The possibility of chain scission during vulcanization was examined by a quantitative analysis of the sol-gel data. Less than 1 site of scission per 100 crosslinked isoprene units was established in the temperature range of 140–200°C. The network results can be satisfactorily correlated with the physical properties of a tyre tread mix of NR as reported in Part 1. Mechanistic interpretations are made to account for the network results.     

Crystallization of vulcanizates. II. Low‐temperature crystallization as a function of extent of cure for polybutadiene vulcanized with dicumyl peroxide,tetramethylthiuram disulfide, 2‐bisbenzothiazole‐2,2′‐disulfide,and zinc–accelerator complexes

Polybutadiene compounds, vulcanized to various degrees of cure, were crystallized in a density column at ?16°C. The percentage crystallinity of vulcanizates was also determined by differential scanning calorimetry where samples, precooled at a programmed rate, were reheated. Curing with peroxides has little effect on either the rate or the extent of crystallization, except at very high crosslink densities, although the induction period prior to crystallization increases progressively with increased crosslink density. Tetramethylthiuram disulfide (TMTD)/sulfur and 2‐bisbenzothiazole‐2,2′‐disulfide (MBTS)/sulfur vulcanizates, cured for progressively longer periods, were found to have lower densities, a result attributed to an increase in free volume occasioned by the formation of accelerator‐terminated pendent groups on the polymer chain. The induction period for crystallization increases and both the rate and the extent of crystallization decrease with extent of cure. These changes are more marked for MBTS vulcanizates that do not crystallize once a gel has formed. Formulations with zinc stearate develop higher crosslink densities and crystallize to a greater extent on cooling, showing the effect of zinc stearate in the crosslinking of pendent groups. The densities of both zinc dimethyldithiocarbamate [Zn₂(dmtc)₄]– and zinc mercaptobenzothiazole [Zn(mbt)₂]–accelerated sulfur vulcanizates increase with cure time, a result attributed to the formation of ZnS in the compounds. Zn₂(dmtc)₄ compounds crystallize extensively on cooling, pointing to limited main‐chain modification. It is suggested that main‐chain modification in these vulcanizates may comprise cyclic sulfide formation. Zn(mbt)₂ compounds crystallize less readily than Zn₂(dmtc)₄ compounds, but to a greater extent than MBTS/sulfur compounds. The crystallization of the vulcanizates is discussed in terms of vulcanization reactions that give rise to crosslinking with the different formulations used. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2573–2586, 2001     

Effect of vulcanization temperature and vulcanization systems on the structure and properties of natural rubber vulcanizates

The effect of vulcanization temperature (150°–180°C) on the structure and technical properties of gum natural rubber vulcanizates with four different 2-(morpholinodithio)-benzothiazole: sulphur ratios (A, 0.6:2.4; B, 1.5:1.5; C, 2.4:0.6; D, 3.0:0.0) at the respective optimum cure times has been determined. The influence of cure temperature on (a) the chemical crosslink density; (b) the distribution of crosslink types; (c) the extent of sulphidic main chain modifications and (d) the zinc sulphide formation was investigated. Results show that elevated cure temperatures produce a network with lower crosslink density, in particular a lower polysulphidic crosslink density. The formation of intramolecular sulphidic groups and zinc sulphide increase with increasing cure temperatures. The possibility of chain scission during vulcanization, as examined by a quantitative analysis of the sol—gel data, was found to be negligible. The network results have been correlated with the technical properties.