Accelerator dithiocarbamate

Ostromow [328] has described the use of conductometry for the analysis of extracts from elastomers and rubbers, such as the determination of various vulcanisation accelerations dithiocarbamates, thiurams (tetramethylthiuramdisulfide, tetramethylthiurammono-sulfide), 2-mercaptobenzothiazole, diphenylguanidine... 

The reaction of carbon disulfide with 1,2-alkylene diamines (I) yields N-(2-aminoethyl) dithiocarbamic acids (II) which split off hydrogen sulfide thermally to give imidazolidine-2-thiones (III) (Hofmann-process). The simplest example, the reaction of carbon disulfide with ethylenediamine, is described in Organic Synthesis (5). The reaction is general for N,N -dialkyl-, N,N -diaryI, as well as for N,N -bis-(arylakyl) ethylene diamines. The rate of reaction is determined by the basicity of the diamine. Electron-donor substituents in the para-position of N-aromatically substituted ethylene diamines accelerate dithiocarbamate formation electron-acceptor groups retard it. 

Previously, accelerators such as thiurams, thiazoles and carbamates were used, but their use has declined because of problems with skin allergies. This issue is discussed in detail by Estlander et al. [6]. In addition to the problems of contact dermatitis, it may be necessary to consider the formation of N-nitrosamines by accelerators. Dithiocarbamates and thiuram sulfides have the potential to decompose to give N-nitrosamine precursors [3]. N-nitrosamines are believed to be carcinogenic, although conclusive evidence for human carcinogenicity is scant, as discussed recently by Loadman [7]. 

Thiuram Sulfides. These compounds, (8) and (9), are an important class of accelerator. Thiurams are produced by the oxidation of sodium dithiocarbamates. The di- and polysulfides can donate one or more atoms of sulfur from their molecular stmcture for vulcanization. The use of these compounds at relatively high levels with litde or no elemental sulfur provides articles with improved heat resistance. The short-chain (methyl and ethyl) thiurams and dithiocarbamates ate priced 2/kg. Producers have introduced ultra-accelerators based on longer-chain and branched-chain amines that are less volatile and less toxic. This development is also motivated by a desire to rninirnize airborne nitrosamines. 

The optimum modulus occurs at about a 2 1 weight ratio of OTOS to OBTS. Similar optimums have been observed with other accelerator combinations. The examples shown in Figure 4 are calculated from regression equations developed from designed experiments in a black-filled natural mbber compound. On a molar basis, the synergistic accelerator complex appears to consist of two dithiocarbamate ligands and one mercaptobenzothiazole moiety, as shown in stmcture (15) (14). 

Fig. 4. Accelerator synergism where A is tetra-/ro-butyl thiuram disulfide and B is zinc di-/ro-butyl dithiocarbamate. To convert MPa to psi, multiply by 145.

It is common practice in the mbber industry for a compounder to use combinations of several accelerators in developing a cure system. Typically these cure systems are comprised of a primary accelerator and one or more secondary types. Primary accelerators are generally the thiazole and sulfenamide classes the secondary types (kickers) are the thiurams, dithiocarbamates, guanidines, and to a much lesser extent, certain amines and the dialkylphosphorodithioates (20). 

Fig. 5. Cure characteristics of accelerators A, thiuram B, dithiocarbamate C, sulfenamide D, thiazole and E, guanidine. The induction period represents...

As a general rule the sulfenamides exhibit faster cure rate than the thiazoles. If secondary accelerators are used, dithiocarbamates are scorchiest and give the fastest cure followed by the thiurams, then the guanidines. Figure 6 summarizes these comparisons to show a series of natural mbber (NR) recipes using either a thiazole (MBTS) or sulfenamide (TBBS) primary accelerator in combination with the various secondary accelerators (21). In this study, the initial primary accelerator levels were selected to produce nearly equivalent modulus or state of cure in the NR. 

Cure Systems of Butyl Rubber and EPDM. Nonhalogenated butyl rubber is a copolymer of isobutjiene with a small percentage of isoprene which provides cross-linking sites. Because the level of unsaturation is low relative to natural mbber or SBR, cure system design generally requites higher levels of fast accelerators such as the dithiocarbamates. Examples of typical butyl mbber cure systems, thein attributes, and principal appHcations have been reviewed (26). Use of conventional and semi-EV techniques can be used in butyl mbber as shown in Table 7 (21). 

Rubber. The mbber industry consumes finely ground metallic selenium and Selenac (selenium diethyl dithiocarbamate, R. T. Vanderbilt). Both are used with natural mbber and styrene—butadiene mbber (SBR) to increase the rate of vulcanization and improve the aging and mechanical properties of sulfudess and low sulfur stocks. Selenac is also used as an accelerator in butyl mbber and as an activator for other types of accelerators, eg, thiazoles (see Rubber chemicals). Selenium compounds are useflil as antioxidants (qv), uv stabilizers, (qv), bonding agents, carbon black activators, and polymerization additives. Selenac improves the adhesion of polyester fibers to mbber. 

Salts of Ai-substituted dithiocarbamic acid [594-07-0] are used as fungicides (qv) and mbber vulcanization accelerators (see Rubber chemicals). 

Accelerators may be added to improve the physical properties of the polymer when needed. Where high modulus or low oil swell is required, thiocarbanihde is the preferred accelerator, with a cure time of 60 min at 100°C. Tetraethyl thiuram disulfide and sodium dibutyl dithiocarbamate are preferred for high tensile strength and cured at 121°C. 

The Goodyear vulcanization process takes hours or even days to be produced. Accelerators can be added to reduce the vulcanization time. Accelerators are derived from aniline and other amines, and the most efficient are the mercaptoben-zothiazoles, guanidines, dithiocarbamates, and thiurams (Fig. 32). Sulphenamides can also be used as accelerators for rubber vulcanization. A major change in the sulphur vulcanization was the substitution of lead oxide by zinc oxide. Zinc oxide is an activator of the accelerator system, and the amount generally added in rubber formulations is 3 to 5 phr. Fatty acids (mainly stearic acid) are also added to avoid low curing rates. Today, the cross-linking of any unsaturated rubber can be accomplished in minutes by heating rubber with sulphur, zinc oxide, a fatty acid and the appropriate accelerator. 

AnUine, however, is too toxic for use in mbber products. Its less toxic reaction product with carbondisulfide, thiocarbanihde, was introduced as an accelerator in 1907. Further developments led to guanidine accelerator [4]. Reaction products formed between carbon disulfide and aliphatic amines (dithiocarbamates) were first used as accelerators in 1919 [5]. These were and still are the most active accelerators in respect to both cross-finking rates and extent of cross-link formation. However, most dithiocarbamates accelerators give little or no scorch resistance and therefore cannot be used in aU applications. 

Increase the rate of the cross-linking action with sulfur considerably allow for lower sulfur content to achieve optimum vulcanisate properties. Organic accelerators (e.g. thiuram, dithiocarbamate, etc.) are of major importance. In some cases it is necessary to retard the onset of vulcanisation to assure sufficient processing safety. The antioxidant 2-mercaptobenzimidazole (MBI) acts as a retarder for most accelerators. 

Zinc dithiocarbamates have been used for many years as antioxidants/antiabrasives in motor oils and as vulcanization accelerators in rubber. The crystal structure of bis[A, A-di- -propyldithio-carbamato]zinc shows identical coordination of the two zinc atoms by five sulfur donors in a trigonal-bipyramidal environment with a zinc-zinc distance of 3.786 A.5 5 The electrochemistry of a range of dialkylthiocarbamate zinc complexes was studied at platinum and mercury electrodes. An exchange reaction was observed with mercury of the electrode.556 Different structural types have been identified by variation of the nitrogen donor in the pyridine and N,N,N, N -tetra-methylenediamine adducts of bis[7V,7V-di- .vo-propyldithiocarbamato]zinc. The pyridine shows a 1 1 complex and the TMEDA gives an unusual bridging coordination mode.557 The anionic complexes of zinc tris( V, V-dialkyldithiocarbamates) can be synthesized and have been spectroscopically characterized.558... 

A class of very fast accelerators for rubber, particularly useful in latex work. The principal member of the class is zinc diethyl dithiocarbamate. 

Organic compounds having four alkyl groups attached to nitrogen. A quaternary ammonium salt is employed in reversing the electric charge on natural rubber latex quaternary ammonium dithiocarbamates are ultra-accelerators for rubber vulcanisation. 

NaHS03, is added to latex from which pale crepe rubber is to be made. It prevents discoloration of the crepe and destroys microorganisms which may cause later deterioration of the rubber. Sodium Dibutyl Dithiocarbamate SDBC, accelerator. 

A term applied to a class of organic accelerators with a very fast and powerful accelerating action examples are the thiuram disulphides, dithiocarbamates and xanthates. See TMT, ZDC and ZIX. 

Amine-activated zinc dibutyl dithiocarbamate, accelerator. 

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