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. 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.     

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.     

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     

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.     

Synthesis of Zn/Mg oxide nanoparticles and its influence on sulfur vulcanization

To reduce the ZnO levels in rubber compounds, mixed metal oxide nanoparticles of zinc and magnesium (Zn_1−xMg_xO) have been synthesized and used as activator. The aim is to obtain better curing properties due to its nanosize and to take advantage of the behavior of both ZnO and MgO in sulfur vulcanization. The model compound vulcanization approach with squalene as a model molecule for NR and CBS as accelerator has been used to study the role of the mixed metal oxide along the reaction. The results found show that with Zn_1–xMg_xO nanoparticles the reaction of CBS becomes faster, higher amounts of MBT are formed at shorter reaction times, and the consumption of sulfur occurs faster in comparison with standard ZnO. Furthermore and more important, an increased crosslink degree calculated as the total amount of crosslinked squalene is obtained. All these findings indicate that Zn_1−xMg_xO is a promising candidate to reduce the ZnO levels in rubber compounds. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Swellability of acrylate methacrylate-cellulose matrix systems and the effect on solute diffusion rates

During the vulcanization of cis-1,4-polyisoprene (IR) with thiruam-related curing systems, dimethyldithiocarbamic acid (DMDCA) is formed as a byproduct, in the formation of either pendent groups or crosslinks. DMDCA is unstable, and decomposes instantly to Me₂NH and CS₂ in the absence of ZnO. The facile reaction of Me₂NH and thiuram-related molecules such as tetramethylthiuram polysulfides, tetramethylthiuram disulfide (TMTD), tetramethylthiuram monosulfide and pendent groups caused (i) increased induction periods, (ii) lower maximum crosslink densities, and (iii) the excessive formation of tetramethylthiourea (TMTU). A most important function of ZnO was to trap the DMDCA via the formation of zinc dimethyldithiocarbamate and water, thereby preventing the detrimental reactions above. The IR/TMTD/ZnO and IR/sulfur/TMTD/ZnO systems were therefore characterized by (i) shorter induction periods, (ii) higher maximum crosslink densities, and (iii) the absence of TMTU.     

The behavior of dithiocarbimate derivative as safety accelerator of natural rubber compounds

A conventional vulcanization system containing tetrabutylammonium bis(4‐methylphenyldithiocarbimato)zincate(II) (ZNIBU) was used for curing of natural rubber (NR) compounds. Rheometric (t_s1, t₉₀, and CRI) and mechanical properties, such as tensile and tear strengths and modulus at 300%, were measured to evaluate the acceleration potential of ZNIBU. Commercial accelerators (TMTD, MBTS, and CBS) and a binary system CBS/ZNIBU were also tested for comparison purposes. It was observed that ZNIBU alone does not give either safe scorch time or cure rates appropriate for industrial applications. Nevertheless, mechanical properties are comparable to those given by the other accelerators used. As for the binary system, positive synergistic effects can be found in tear strength and modulus of NR vulcanizates. Besides, ZNIBU does not contribute for the formation of nitrosamines in the vulcanization process. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

New mechanism for the reaction of amines with zinc dithiocarbamates

This article reports a detailed reinvestigation of the reaction of bis(dialkyldithiocarbamato)zinc(II) (ZDAC) with amines. The reaction of primary amines with bis(dimethyldithiocarbamato)zinc(II) (ZDMC) results in the formation of a 1,1,3‐trisubstituted thiourea, a 1,3‐disubstituted thiourea, dimethylammonium dimethyldithiocarbamate (DMADC), ZnS, and H₂S. The ratio of formation between the two thiourea products strongly depends on the reaction conditions chosen. A new mechanism is proposed, which involves the formation of an amine–dithiocarbamic intermediate, from which the two most important products, a 1,1,3‐trisubstituted and a 1,3‐disubstituted thiourea, are formed. Also, direct transformation of the 1,1,3‐trisubstituted thiourea into the 1,3‐disubstituted thiourea via nucleophilic attack of the primary amine onto the thiocarboxy of the 1,1,3‐trisubstituted thiourea was found to occur, catalyzed by ZnCl₂. The reaction of primary amines with ZDACs is catalyzed by elemental sulfur, which has been attributed to sulfur insertion in the zinc–ligand ring of the ZDAC, resulting in a higher reactivity of the ZDAC complex. Finally, when ZDACs are reacted with a secondary amine, no thiourea products are formed and only a mixture of zinc dithiocarbamates is obtained. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1074–1083, 2001     

Novel dynamic vulcanization of polyethylene and ozonolysed natural rubber blends: Effect of curing system and blending ratio

Dynamic vulcanization was studied in terms of the change in α‐relaxation temperatures of the LDPE matrix, morphology, and mechanical properties of LDPE/ozonolysed NR blends which were vulcanized at various blend ratios and with different curing systems, i.e., peroxide and sulfur systems. The ozonolysed NR with M _w = 8.30 × 10⁵ g mol⁻¹ and M _n = 2.62 × 10⁵ g mol⁻¹, prepared by the in situ ozonolysis reaction of natural rubber latex, was used in this study. The significant change in the α‐relaxation temperature of LDPE in the LDPE/ozonolysed NR, dynamically vulcanized using the sulfur system, suggested that sulfur vulcanization of the blend gave a higher degree of crosslink density than using peroxide and corresponded with the improved damping property and homogenous phase morphology. However, the peroxide cured blends of LDPE/ozonolyzed NR gave more improvement of tensile strength and elongation at break than the sulfur cured system. Furthermore, the mechanical properties of tensile strength, elongation at break, and damping were improved by increasing the ozonolyzed natural rubber content in both DCP and sulfur cured blends. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Vulcanization kinetics of low‐protein natural rubber with use of a vulcameter

Kinetics of vulcanization of low‐protein natural rubber (LPNR) was studied with the use of a vulcameter. In the induction period of vulcanization, the time t₀ of LPNR is longer than that of natural rubber (NR), and the temperature dependences of the time t_dis and the rate constant of LPNR are greater than that of NR. Both the curing periods of LPNR and NR (except 170°C for LPNR) consist of two stages. The first stage follows first‐order reaction. The rate constant k₂ of LPNR in the first stage is substantially the same as that of NR at the same temperature, and so is the activation energy E₂. The second stage (end stage of the curing period) does not follow first‐order reaction, and the calculated reaction order n is in the range of 0.67–0.73. Both rate constants of LPNR (except 170°C) and NR at the same temperature are approximately the same, and so is the activation energy E_3. The whole process of curing period for LPNR at 170°C follows n = 0.7 order reaction. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Effect of water and hydrogen sulfide in zinc dimethyldithiocarbamate accelerated sulfur vulcanization

Rubber and the model compound 2,3‐dimethyl‐2‐butene (TME) are vulcanized with zinc dimethyldithiocarbamate [Zn₂(dmtc)₄] accelerated sulfur formulations. When heated in dry nitrogen, Zn₂(dmtc)₄ is stable at vulcanization temperatures. However, it shows a mass increase when heated in moist nitrogen, indicating strong coordination with water; in a nitrogen/H₂S atmosphere rapid degradation to dimethyldithiocarbamic acid (Hdmtc) and ZnS occurs. Model compound studies show that crosslinked sulfides are essentially bis(alkenyl) and confirm the absence of accelerator terminated pendant groups in the vulcanizates, while the ease with which rubber vulcanizates crystallize on cooling in a density column also suggests that pendant groups are largely absent. However, the rates of crystallization, measured as the time for the crystallization process to go to 50% completion, are slower in lightly crosslinked gels than in peroxide cures of similar crosslink density, particularly in the vulcanizates cured in a vacuum; this is interpreted as an indication that some residual pendant groups are present in Zn₂(dmtc)₄ vulcanizates. Water promotes the rate of crosslink formation in both rubber and TME systems, and it is suggested that the strong coordination of water with zinc in Zn₂(dmtc)₄ promotes its reactivity. The H₂S liberated in the vulcanization process promotes decomposition of Zn₂(dmtc)₄ to Hdmtc, and this reaction makes an important contribution to the amount of Hdmtc that is formed in situ. The importance of Hdmtc as an accelerator and its role in providing alternative routes to crosslink formation in Zn₂(dmtc)₄ accelerated sulfur vulcanization are discussed. It is suggested that water, which is liberated when Hdmtc reacts with ZnO to form Zn₂(dmtc)₄, activates newly formed Zn₂(dmtc)₄ molecules; and this accounts for the beneficial influence of ZnO in Zn₂(dmtc)₄ formulations. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1516–1531, 2002     

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     

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     

N,N′‐Pentamethylenethiuram disulfide‐ and N,N′‐pentamethylenethiuram hexasulfide‐accelerated sulfur vulcanization. I. Interaction of curatives in the absence of rubber

N,N′‐pentamethylenethiuram disulfide (CPTD), CPTD/sulfur, and N,N′‐pentamethylenethiuram hexasulfide (CPTP6) were heated in a DSC at a programmed heating rate and isothermally at 140°C. Residual reactants and reaction products were analyzed by HPLC at various temperatures or reaction times. CPTD rapidly formed N,N′‐pentamethylenethiuram monosulfide (CPTM) and N,N′‐pentamethylenethiuram polysulfides (CPTP) of different sulfur rank, CPTP of higher sulfur rank forming sequentially, as reported earlier for tetramethylthiuram disulfide (TMTD). As with TMTD, the high concentration of the accelerator monosulfide that develops is attributed to an exchange between CPTD and sulfenyl radicals, produced on homolysis of CPTD. However, a different mechanism for CPTP formation to that suggested for TMTD is proposed. It is suggested that disulfenyl radicals, resulting from CPTM formation, exchange with CPTD and/or CPTP already formed, to give CPTP of higher sulfur rank. CPTD/sulfur and CPTP6 very rapidly form a similar product spectrum with CPTP of sulfur rank 1–14 being detectable. Unlike with TMTD/sulfur, polysulfides of high sulfur rank did not form sequentially when sulfur was present, CPTP of all sulfur rank being detected after 30 s. It is proposed that sulfur adds directly to thiuram sulfenyl radicals. Recombination with sulfenyl radicals, which would be the most plentiful in the system, would result in highly sulfurated unstable CPTP. CPTP of higher sulfur rank are less stable than are disulfides as persulfenyl radicals are stabilized by cyclization, and the rapid random dissociation of the highly sulfurated CPTP, followed by the rapid random recombination of the radicals, would result in the observed product spectrum. CPTP is thermally less stable than is TMTD and at 140°C decomposed rapidly to N,N′‐pentamethylenethiourea (CPTU), sulfur, and CS₂. At 120°C, little degradation was observed. The zinc complex, zinc bis(pentamethylenedithiocarbamate), did not form at vulcanization temperatures, although limited formation was observed above 170°C. ZnO inhibits degradation of CPTD to CPTU. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2718–2731, 2000     

Polybutadiene rubber/organoclay nanocomposites: Effect of organoclay with various modifier concentrations on the vulcanization behavior and mechanical properties

It has been reported that the cure time t₉₀, scorch time t₂, and their difference (t₉₀?t₂) of Polybutadiene rubber (BR)/organoclay nanocomposites were much reduced over those of BR. This effect can be attributed to the ammonium groups in the organoclay. The possible formation of a Zn complex in which sulfur and ammonium modifier participate may facilitate the formation of crosslinks. If this assumption is true, it is expected that the organoclay with higher ammonium modifier concentration will give larger torque difference and faster vulcanization rate to the BR/organoclay nanocomposites. The effect of organoclay with different modifier concentration on the vulcanization behavior and mechanical properties of BR/organoclay hybrid was investigated in this study. As expected, the order of the torque difference was BR/Cloisite 15A > BR/Cloisite 10A > BR/Cloisite 20A > BR/Cloisite 25A > BR/Cloisite 30B > BR/Cloisite Na⁺, and the order of vulcanization rate also showed similar trends. The organoclay with higher modifier concentration gave larger torque difference and faster vulcanization rate to the BR/organoclay nanocomposites. POLYM. ENG. SCI., 47:308–313, 2007. © 2007 Society of Plastics Engineers.     

Structural characterization of vulcanizates. Part IX. Comparison of the vulcanization of natural rubber and cis-trans-isomerized natural rubber with sulfenamide-accelerated sulfur and dicumyl peroxide vulcanization systems

Large variations in the microstructure of 1,4-polyisoprenes, from ca. 100% cis-trialkylethylene groups, as in natural rubber (NR), to ca. 40% cis- and 60% trans-trialkylethylene groups, as in an equilibrium-isomerized NR, have little influence on the overall chemistry of vulcanization of the polyisoprenes by a N-cyclohexylbenzothiazole-2-sulfenamide-accelerated sulfur system or by a dicumyl peroxide system. The peroxide crosslinks the equilibrium-isomerized NR more efficiently than it crosslinks NR; this is attributed to the sulfur dioxide, which is used to isomerize the NR, scavenging some of the nonrubber constituents in the NR, which are known to compete with the rubber hydrocarbon for reaction with free radicals from the peroxide. By comparison with NR vulcanizates, the corresponding equilibrium-isomerized NR vulcanizates have higher values of the C₂ term of the Mooney-Rivlin stress–strain equation and higher χ (polymer–swelling liquid interaction parameter) values of the Flory-Huggins equation.     

Effect of non‐rubber substances on vulcanization kinetics of natural rubber

Effect of non‐rubber components on vulcanization kinetics of natural rubber was studied with the use of a Rheometer MDR‐2000. The results show that the rate constants of induction period and curing period of natural rubber (NR) are greater than that of natural rubber extracted with acetone (NR_E), and the activation energies of induction period and curing period of NR are lower than that of NR_E. The activation energy of induction period of NR is reduced by16.9% and the activation energy of curing period of NR is reduced by 3.2% compared to the activation energies of NR_E. The time t_dis of NR is shorter than that of NR_E at the same temperature. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

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.     

Influence of sulfenamide accelerators on cure kinetics and properties of natural rubber foam

The effect of types of sulfenamide accelerator, i.e., 2‐morpholinothiobenzotiazole (MBS), N‐t‐butylbenzothiazole‐2‐sulfenamide (TBBS), and N‐cyclohexyl benzothiazole‐2‐sulfenamide (CBS) on the cure kinetics and properties of natural rubber foam was studied. It has been found that the natural rubber compound with CBS accelerator shows the fastest sulfur vulcanization rate and the lowest activation energy (E_a) because CBS accelerator produces higher level of basicity of amine species than other sulfenamide accelerators, further forming a complex structure with zinc ion as ligand in sulfur vulcanization. Because of the fastest cure rate of CBS accelerator, natural rubber foam with CBS accelerator shows the smallest bubble size and narrowest bubble size distribution. Moreover, it exhibits the lowest cell density, thermal conductivity and thermal expansion coefficient, as well as the highest compression set as a result of fast crosslink reaction. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44822.