A study of curative interactions in cis-1,4-polyisoprene. X. The cis-1,4-polyisoprene/sulfur/zinc dimethyldithiocarbamate and cis-1,4-polyisoprene/sulfur/zinc dimethyldithiocarbamate/ZnO systems

Aspects of the mechanism of zinc dimethyldithiocarbamate (ZDMC)-accelerated sulfur vulcanization were discussed. The trends in the efficiency parameter E, confirmed that crosslinking is preceded by the formation of pendent groups RS_xSX [R = polyisoprenyl, X = Me₂NC(S)] in ZDMC-based systems. The index x in RS_xX was calculated as 5.82 in the cis-1,4-polyisoprene (IR)/sulfur/ZDMC/ZnO compound at the initial stages of curing, compared to 3.23 in the absence of ZnO. The high value of x supports the postulation that elemental sulfur and ZDMC react at the early stages of vulcanization, to form the active sulphurating agent XS_xSZnSSX. Crosslinks form by either a disproportionation reaction between two α-methylic or α-methylenic pendent groups RS_xX, or a reaction between a pendent group RS_xX and the rubber chain—these routes are the same as that suggested for the IR/tetramethylthiuram disulfide (TMTD)/ZnO compound. The beneficial role of ZnO and zinc stearate is shown, as in the case of ZnO in the IR/TMTD/ZnO system, to be related to their ability to trap dimethyldithiocarbamic acid, which formed in the generation of pendent groups and crosslinks. ZnS is inactive in this regard. The formation of ZnS is characteristic of natural rubber/sulfur/ZDMC/ZnO systems, as opposed to IR/TMTD/ZnO mixtures where little ZnS forms.     

Study of curative interactions in cis-1,4-polyisoprene. VI. Interaction of some combinations of sulfur,tetramethylthiuram disulfide,and ZnO

The interaction of curatives in the systems cis-1,4-polyisoprene (IR)–sulfur, IR–sulfur–ZnO, IR–tetramethylthiuram disulphide (TMTD), and IR–sulfur–TMTD were studied. Thermal events observed in the differential scanning calorimetry curing curves characteristic of these systems were explained in terms of the melting/liquefaction of compounds, the evaporation of gases, and the vulcanization process itself. The similarity of the IR–sulfur and IR–sulfur–ZnO curing curves suggested that sulfur and ZnO were unreactive during vulcanization. On heating the IR–TMTD and IR–sulfur–TMTD systems, gases such as Me₂NH and CS₂ formed easily. Although the maximum crosslink densities in the latter systems were low, the crosslink formation was found to be strongly exothermic. The sulfur efficiency parameter E was estimated for the IR–sulfur–TMTD system and decreased steeply from 37.5 (at 143.2°C) to 16.6 (at 151.0°C). This was taken as evidence that much of the bound sulfur was initially combined in pendent groups. Then E increased dramatically toward the advanced stages of cure, emphasizing the extraordinary inefficient manner in which sulfur was utilized to form crosslinks.     

Study of curative interactions in cis-1,4-polyisoprene (IR). VII. The cis-1,4-polyisoprene–tetramethylthiuram disulfide–ZnO system

A detailed account of the mechanism of crosslinking in the cis-1,4-polyisoprene (IR)-tetramethylthluram disulfide (TMTD)–ZnO system is given. Many experimental observations were harmonized in terms of a radical mechanism, rather than an ionic mechanism. Electron spin resonance (ESR) spectra on the IR–TMTD–ZnO system, recorded at 120°C, inter alia revealed resonance lines in the vicinity of g = 2.02. These were related to the rapid formation of thiuram persulphenyl radicals XS, on the homolytic splitting of tetramethylthiuram polysulfides. The Moore–Trego efficiency E dropped from 11.5 (at 140.0°C) to 3.5 (at 146.9°C), indicating that a substantial part of the sulfur atoms was initially to be associated with pendent groups. The formation of these pendent groups could be viewed as an irreversible, concerted reaction without the formation of a true alkenyl radical intermediate. Crosslinks would form by either a disproportionation reaction between two α-methylic or α-methylenic pendent groups RS_xX or a reaction between a pendent groups RS_xX (R = polyisoprenyl, x ≥ 2, X = Me₂NC(S)) and the unsaturated polymer chain. The latter crosslink formation reactions were regarded as rate determining in the vulcanization sequence. A mechanism is proposed that does not require the participation of ZnO in the formation of the active sulfurating agent.     

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.     

Study of curative interactions in cis-1,4-polyisoprene (IR). V. General experimental procedure

The tetramethylthiuram disulfide (TMTD) and zinc dimethyldithiocarbamate (ZDMC) related vulcanization of cis-1,4-polyisoprene (IR) were studied by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and electron spin resonance (ESR). The progress of the reactions in a given compound was monitored by analyzing the vulcanizate at selected points along the DSC curing curve. Full details of the analysis procedures are given. Analysis were mainly concerned with measurement of the crosslink densities, percentage of polysulfidic crosslinks, and the types and quantities of extractable compounds by thin layer chromatography (TLC) and high-performance liquid chromatography (HPLC).     

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.     

Bis(diisopropyl) thiophosphoryl disulfide in cis-1,4-polyisoprene vulcanization reactions. I. As a sulfur donor

Bis(diisopropyl)thiophosphoryl disulfide (DIPDIS) is used as a sulfur donor vulcanizing system for cis-1,4-polyisoprene. It is shown that the network structure consists of poly- and disulfidic crosslinks at early stages of cure, simplifying at optimum cure to monosulfidic crosslinks. It is thought that pendent accelerator groups are bound to the rubber molecule at early stages of cure, but are subsequently replaced by cyclic sulfidic groups. The good thermal and thermal oxidative aging behaviour of the vulcanizate is due to the formation of zinc diisopropyldithiophosphate (ZDP) in situ.     

A study of the rate of formation of polysulfides of tetramethylthiuram disulfide

The rate of formation of tetramethylthiuram polysulfides (TMTP), that play an important role in vulcanization, was studied. After a short induction period (<30 s), tetramethylthiuram disulfide (TMTD) and TMTD-sulfur mixes, heated to 130–150°C in the absence of rubber, rapidly form a series of TMTPs. The concentrations of TMTPs of lower sulfur rank increase most rapidly, indicating that sulfur atoms are added to the accelerator sequentially. The incorporation of sulfur molecules to give TMTPs, which subsequently desulfurate, does not occur. Equilibrium concentrations of the various TMTPs are achieved in about 2 min. Little tetramethylthiourea is formed below 200°C. Tetramethylthiuram monosulfide (TMTM) is stable, but TMTM-sulfur mixes form TMTPs. A mechanism is proposed to account for the large amount of TMTM formed on heating TMTD in the absence of sulfur and the correspondingly higher TMTP concentrations in the presence of sulfur. © 1995 John Wiley Sons, Inc.     

Reclamation of vulcanized rubbers by chemical degradation. VIII. Absorption of oxygen and degradation of cis-1,4-polyisoprene by phenylhydrazine–iron(II) chloride system

Absorption of oxygen and degradation of cis-1,4-polyisoprene by the phenylhydrazine–iron(II) chloride system was investigated at 30°C in connection with the mechanism of reclamation of vulcanized rubbers by the system. In the presence of iron(II) chloride, phenylhydrazine rapidly absorbed an equimolar amount of oxygen and evolved an equimolar amount of nitrogen. Gas-chromatographic analysis of the reaction mixture showed the presence of benzene, phenol, and biphenyl in 37%, 35–60%, and 4–8% yields, respectively, based on phenylhydrazine. When cis-1,4-polyisoprene was added to the reaction mixture, additional absorption of oxygen was observed. Molecular weight of the polymer decreased during the oxygen absorption, and the scission efficiency (i.e., number of mole scissions/mole oxygen) was 0.14–0.26.     

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     

A DSC study of curative interactions. I. The interaction of ZnO,sulfur, and stearic acid

The interaction between combinations of sulfur, stearic acid, and ZnO were studied by differential scanning calorimetry in the absence of rubber. The only reaction observed was between ZnO and stearic acid. A small amount of zinc stearate formed as soon as the stearic acid melted, but the solid product blocked further reaction, which was only completed at 154°C. Water played a major role in the reaction, and in the presence of water, the reaction went to completion at lower temperatures. Sulfur, too, affected the temperature of the ZnO/stearic acid reaction. The preparation of zinc stearate by a number of routes was investigated.     

A DSC study of curative interactions. III. The interaction of TMTM with ZnO,sulfur, and stearic acid

The interaction among various combinations of sulfur, tetramethylthiuram monosulphide (TMTM), ZnO, and stearic acid were studied by differential scanning calorimetry in the absence of rubber. Sulfur and TMTM reacted to form tetramethylthiuram disulphide, and the ternary eutectic mixture melted at about 80°C. The absence of the S_γ → S_μ transition in sulfur/TMTM mixes was related to a sulfur/TMTM interaction, wherein the eightmembered sulfur rings were opened at temperatures well below 170°C. The interaction of stearic acid with TMTM led to the decomposition of TMTM, but the reaction was largely suppressed when both ZnO and sulfur were present in the mixture. No evidence was found for the formation of a zinc-accelerator complex of the type normally attributed a role in the accelerated sulfur vulcanization.     

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     

Comparison of tetraethyl‐ and tetramethylthiuram disulfide vulcanization. I. Reactions in the absence of rubber

The reactions of tetraethylthiuram di‐ and monosulfide (TETD and TETM, respectively) were investigated in the absence of rubber and compared with those reported previously for tetramethylthiuram compounds. The reactions of TETM, TETD, and zinc diethyldithiocarbamic acid with zinc oxide and sulfur were investigated by differential scanning calorimetry, and the reaction products analyzed by high performance liquid chromatography. TETM was shown to be more stable at vulcanization temperatures (±150°C), but also less reactive with sulfur than tetramethylthiuram disulfide (TMTD). The reactions of TETD are very similar to those of TMTD, the TETD reacting slower than the TMTD to form analogous products. In the presence of zinc oxide, the formation of the zinc compound of TETD, zinc diethyldithiocarbamic acid, occurred readily. TMTD does not react readily with zinc oxide. The reaction of TETD with sulfur lead to the formation of polysulfidic accelerator species, although the concentrations formed in the absence of rubber were considerably less than that formed by the corresponding TMTD system. These differences in reactivity would affect the vulcanization reactions that take place in the rubber. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2292–2299, 2001     

A DSC study of curative interactions. II. The interaction of 2,2′-dibenzothiazole with ZnO,sulfur, and stearic acid

The interaction of combinations of sulfur, 2,2′-dibenzothiazole (MBTS), ZnO, and stearic acid were studied by differential scanning calorimetry. A MBTS/stearic acid interaction was indicated as evidenced by the effect the MBTS/stearic acid combination had on the melting of sulfur, the S_α → S_β transition being suppressed in favor of a S_α → S_γ transition. The dissolution/interaction of MBTS in molten sulfur was also delayed by the MBTS/stearic acid interaction, which, it is proposed, involved protonation of the N atom in MBTS by stearic acid. MBTS did not affect the formation of zinc stearate from ZnO and stearic acid, but when sulfure was added to the mixture, the ZnO/stearic acid reaction did not go to completion. No direct evidence for the formation of 2,2′-dibenzothiazole polysulphides was found, but the absence of the S_γ → S_μ transition in sulfur/MBTS mixes was interpreted as indirect evidence of a reaction between these curatives. There was no evidence for the formation of a sulfur/MBTS/ZnO compound of the type generally attributed the role of an active sulfurating agent in accelerated sulfur vulcanization.     

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.     

A study of curative interactions in the presence of cobalt(II) stearate

The curative interactions with the participation of dicyclohexylbenzothiazole‐2‐sulfenamide (DCBS), stearic acid (SA), ZnO, S, and Co(II) stearate (octadecanoate‐CoC₁₈) as adhesive promoter have been investigated by means of DSC calorimetry, EPR, and IR spectroscopy in the absence of rubber. It has been found that in the presence of CoC₁₈, DCBS, and S, structural changes have been observed on the action of heat, which are connected with the formation of polysulfide complexes between Co²⁺ ions, DCBS fragments, and sulphur. In the presence of SA and ZnO in the five‐component system, zinc(II) octadecanoate is formed. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2936–2943, 2001     

Contribution to the mechanism of the thiuram vulcanization. I. Polymerization of styrene in the presence of tetramethylthiuram disulfide and natural rubber

The influence of the concentration of tetramethylthiuram disulfide (TMTD) on grafting of natural rubber by styrene at 80°, 95°, 115°, and 130°C and constant molar ratio of rubber and styrene was studied. It was found that the dependence R_p = f([TMTD]^½) at all followed temperatures goes through a maximum and that TMTD substantially decreases the amount of bound rubber in the graft copolymer. The analysis of the kinetic data and the results of separation of polymer mixtures showed the significant role in the process of the termination reactions of the growing polymer and the rubber radicals with the RS radicals. The derived kinetic relation is in good agreement with the experimental, results and allows calculation of the transfer rate constants of RS radical on rubber.     

Role of stearic acid in the strain-induced crystallization of crosslinked natural rubber and synthetic cis-1,4-polyisoprene

Strain-induced crystallization of crosslinked natural rubber (NR) and its synthetic analogue, cis-1,4-polyisoprene (IR), both mixed with various amounts of stearic acid (SA), were investigated by time-resolved X-ray diffraction using a powerful synchrotron radiation source and simultaneous mechanical (tensile) measurement. No acceleration or retardation was observed on NR in spite of the increase of SA amount. Even the SA-free IR crystallized upon stretching, and the overall crystallization behavior of IR shifted to the larger strain ratio with increasing SA content. No difference due to the SA was detected in the deformation of crystal lattice by stress for both NR and IR. These results suggested that the extended network chains are effective for the initiation of crystallization upon stretching, while the role of SA is trivial. These behaviors are much different from their crystallization at low temperature by standing, where SA acts as a nucleating agent.