Thiuram disulfides

Piperidines. A significant use of piperidine (18) has been ia the manufacture of vulcanization accelerators, eg, thiuram disulfide [120-54-7] (115) (see Rubber chemicals). Mepiquat dichloride [24307-26-4] the dimethyl quaternary salt of (18), is used as a plant growth regulator for cotton (qv). Piperidine is used to make vasodilators such as dipyridamole [58-32-2] (116) and minoxidil [38304-91-5] (117), and diuretics such as etozoline [73-09-6] (118). 

Sulfur Donors. MBSS, DPTH, and the thiuram disulfides (see Table 2) ate examples. The morpholine disulfide and caprolactam disulfide examples in Table 4 can also donate one atom of sulfur from their molecular stmcture for cross-linking purposes. Monosulfide cross-links provide better thermal stabiUty than the sulfur—sulfur bonds in di- and polysulfide cross-links, which predominate when elemental sulfur is used. 

Dimercapto-l,3,4-thiadiazole derivatives, accelerated by amines, are used to cross-link chlorinated polyethylene. Polyisobutylene containing brominated i ra-methylstyrene cure functionahty can be cross-linked in polymer blends with dimercapto-1,3,4-thiadiazole derivatives accelerated with thiuram disulfides. Trithiocyanuric acid is suggested for use in polyacrylates containing a chlorine cure site and in epichlorohydrin mbbers. 

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.

Monomer conversion (79) is followed by measuring the specific gravity of the emulsion. The polymerization is stopped at 91% conversion (sp gr 1.069) by adding a xylene solution of tetraethylthiuram disulfide. The emulsion is cooled to 20°C and aged at this temperature for about 8 hours to peptize the polymer. During this process, the disulfide reacts with and cleaves polysulfide chain segments. Thiuram disulfide also serves to retard formation of gel polymer in the finished dry product. After aging, the alkaline latex is acidified to pH 5.5—5.8 with 10% acetic acid. This effectively stops the peptization reaction and neutralizes the rosin soap (80). 

Curing Systems. Polychloroprene can be cured with many combiaations of metallic oxides, organic accelerators, and retarders (114). The G family of polymers, containing residual thiuram disulfide, can be cured with metallic oxides alone, although certain properties, for example compression set, can be enhanced by addition of an organic accelerator. The W, T, and xanthate modified families require addition of an organic accelerator, often ia combination with a cure retarder, for practical cures. 

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. 

It was found that a high-impact strength is obtained in PP-EPDM blends by slow curing with sulfur. Thiuram disulfide N-(cyclohexylthio)phthalimide was used as an inhibitor of curing, and its effect on the impact strength of dynamically cured PP-EPDM blends was studied (Table 6). It was also found that the one-step method of blend preparation also has a favorable effect on the impact strength of the resultant blend system. 

All compositions contain EPDM, 100 phr zinc oxide, 5 phr stearic acid, 1 phr antioxidant, 1 phr 2-mercaptobenzothiazole (accelerator), 1.5 phr tetramethyl thiuram disulfide (accelerator), 1 phr and sulfur, 1.5 phr. 

In dithiocarbamato complexes such an ambiguity can only occur when at least two dithiocarbamato ligands are bonded to a metal. In that case the question arises whether the compound is a bis (dithiocarbamato) or a thiuram disulfide complex. In these two types of complexes the oxidation number of the metal differs 2 units. 

Interesting compounds are [Cr(R4rinfrared spectra indicate that these complexes are not Cr(V) dithiocarbamato complexes but rather Cr(III) compounds with coordinated thiuram disulfide. As will be shown, thiuram disulfide can oxidise Cu, Ag and Au to M(II) and M(III) dithiocarbamato complexes. The Cr(III)-thiuram disulfide combination seems to be stable, just like the thiuram disulfide combination with Zn, Cd, and Hg. 

The MofVJ compounds [Mo(R2cffc)4]X can be prepared by oxidative addition of thiuram disulfide to molybdenum carbonyls or by mild oxidation of Mo(R2C fc)4. 

Excessive halogenation of several dithiocarbamato and thiuram disulfide complexes yields compounds in which the ligand is oxidised to the dipositive 3,5-Ris (N,N dialkyl/minium) frifhio-... 

The reaction of metallic copper with thiuram disulfides yields complexes of Cu I), which are polymeric in solution as well as in the solid state 121,122). In 123) the copper atoms are located at the corners of a slightly distorted tetrahedron with Cu—Cu distances ranging from 2.6—2.7 A. Each of the copper atoms is coordinated to three sulfur atoms in a nearly planar triangular arrangement and each sulfur atom coordinates one or two copper atoms. 

Oxidation of these complexes with halogen results in the oxidation of the ligand, yielding a thiuram disulfide complex X2M(R4tds), leaving the oxidation state of the metal unchanged (99,100,161). 

The other two CEN standards, for the determination of dithiocarbamate/thiuram disulfide residues and for the quantitation of bromide, are also separated into parts, but, in contrast to the multi-residue methods, complete methods are presented in each different part. Owing to this different approach and the reduced number of analytes, it was possible to validate these methods fully. 

Table 7 Presentation of the validation results in EN 13191 2000 Nonfatty foods - Determination of dithiocarbamate and thiuram disulfide residues - Part 1 ...

FDMPTD Dimethyl-di-(p-fluorophenyl)-thiuram disulfide L Ligand... 

Examples in organometallic systems are known. Reaction of thiuram disulfides, (R2NCS2)2, with Co(Cp)(CO)2 produces dithiocarbamato pseudo-octahedral cobalt(III) complexes Co(Cp)(dtc)2 with one chelated and one monodentate dtc, also accessible via Co(Cp)I(dtc).1050 Fluxional behavior, including monodentate chelate exchange, was observed for some complexes in temperature-dependent NMR studies. The Co(Cp)I(dtc) complex was defined in a crystal structure. 

Nair et al. studied the kinetics of the polymerization of MMA at 60-95 °C using N,1SP-diethyl-NjW-di(hydroxyethyl)thiuram disulfide (30a) as the thermal in-iferter [142]. The dependence of the iniferter concentration on the polymerization rate was examined. The chain transfer constant of the propagating radical of MMA to 30a was determined to be 0.23-0.46 at 60-95 °C, resulting in the activation energy of 37.6 kj/mol for the chain transfer. Other derivatives 30b-30d were also prepared and used to derive telechelic polymers with the terminal phosphorus, amino, and other functional aromatic groups [143-145]. Thermal polymerization was also investigated with the end-functional poly(St) and poly(MMA) which were prepared using the iniferter 13 [146]. 

Since isolable organocopper) 11) compounds do not apparently exist, it is rather surprising that oxidation of the cuprate CdI+[(CF3)2Cu ] (prepared in situ) with thiuram disulfide affords (CF3)2Cu "S2CNEt2 (see Eqn. 1 in Scheme 1.6), the first and so far only example of an organocopper compound with the copper atom in the trivalent oxidation state. The structure of this compound was unambiguously proven by an X-ray crystal structure determination (see Fig. 1.2) [37]. 

Ethylene thiram disulfide, see Thiram Ethylene thiuram disulfide, see Ferbam. Mancozeb Ethylene thiuram monosulfide, see Ferbam. Mancozeb. Maneb... 

CASRN 14484-64-1 molecular formula CgHisFeNsSe FW 416.50 Plant. Decomposes in plants to ethylene thiourea, ethylene thiuram monosulfide, ethylene thiuram disulfide, and sulfur (Hartley and Kidd, 1987). 

Captax (Structure 15.21) is used to the extent of 1% with hevea rubber and accounts for the major part of the over 30,000 t of accelerators used annually in the United States. Other accelerators widely used include 2-mercaptobenzothiazole sulfenamide (Santocure Structure 15.22), used for the vulcanization of SBR dithiocarbamates and thiuram disulfides. Thiuram disulfide (Structure 15.23) is a member of a group called ultra-accelerators, which allow the curing of rubber at moderate temperatures and may be used in the absence of sulfur. 

---