Mercaptides

Preparation of 2 4-dinitrophenyl-sulphides. Dissolve about 0-5 g. (or 0 005 mol) of the mercaptan in 10-15 ml, of rectified spirit (or in the minimum volume necessary for solution warming is permissible) and add 2 ml. of 10 per cent, sodium hydroxide solution. Mix the resulting sodium mercaptide solution with a solution of 1 g. of 2 4-dinitrochlorobenzene in 5 ml. of rectified spirit. Reaction may occur immediately with precipitation of the thioether. In any case reflux the mixture for 10 minutes on a water bath in order to ensure the completeness of the reaction. Filter the hot solution rapidly allow the solution to cool when the sulphide will crystaUise out. RecrystaUise from alcohol. 

The reaction with sodium sulfite or bisulfite (5,11) to yield sodium-P-sulfopropionamide [19298-89-6] (C3H7N04S-Na) is very useful since it can be used as a scavenger for acrylamide monomer. The reaction proceeds very rapidly even at room temperature, and the product has low toxicity. Reactions with phosphines and phosphine oxides have been studied (12), and the products are potentially useful because of thek fire retardant properties. Reactions with sulfide and dithiocarbamates proceed readily but have no appHcations (5). However, the reaction with mercaptide ions has been used for analytical purposes (13)). Water reacts with the amide group (5) to form hydrolysis products, and other hydroxy compounds, such as alcohols and phenols, react readily to form ether compounds. Primary aUphatic alcohols are the most reactive and the reactions are compHcated by partial hydrolysis of the amide groups by any water present. 

Organotia mercaptides can also absorb hydrogen chloride. 

Replacement of Labile Chlorines. When PVC is manufactured, competing reactions to the normal head-to-tail free-radical polymerization can sometimes take place. These side reactions are few ia number yet their presence ia the finished resin can be devastating. These abnormal stmctures have weakened carbon—chlorine bonds and are more susceptible to certain displacement reactions than are the normal PVC carbon—chlorine bonds. Carboxylate and mercaptide salts of certain metals, particularly organotin, zinc, cadmium, and antimony, attack these labile chlorine sites and replace them with a more thermally stable C—O or C—S bound ligand. These electrophilic metal centers can readily coordinate with the electronegative polarized chlorine atoms found at sites similar to stmctures (3—6). 

Stabilizer Synthesis. The selected alkyltin chloiide intermediate reacts with either a carboxyhc acid or a mercaptan in the presence of an appropriate base, such as sodium hydroxide, to yield the alkyltin carboxylate or alkyltin mercaptide heat stabihzet. Alternatively, the alkyltin chloride can react with the base to yield the alkyltin oxide, which may or may not be isolated, for subsequent condensation with the selected carboxyhc acid or mercaptan. 

Cost bilizers. In most cases the alkyl tin stabilizets ate particularly efficient heat stabilizers for PVC without the addition of costabilizers. Many of the traditional coadditives, such as antioxidants, epoxy compounds, and phosphites, used with the mixed metal stabilizer systems, afford only minimal benefits when used with the alkyl tin mercaptides. Mercaptans are quite effective costabilizets for some of the alkyl tin mercaptides, particularly those based on mercaptoethyl ester technology (23). Combinations of mercaptan and alkyl tin mercaptide ate currendy the most efficient stabilizers for PVC extmsion processes. The level of tin metal in the stabilizer composition can be reduced by up to 50% while maintaining equivalent performance. Figure 2 shows the two-roU mill performance of some methyl tin stabilizers in a PVC pipe formulation as a function of the tin content and the mercaptide groups at 200°C. 

Fig. 2. Yellowness index vs two-roU mill heat stabiUty, where the mercaptide ligands, — SCH2COOR (A), —SCH2CH2COOR ( ), and —SCH2CH2C00R + HSCH2CH2C00R ( )) IT 9, and 6% Sn, respectively. R = CgH. R = H33. ...

The various lubricants formulated into PVC to improve the processing can also enhance the performance of the stabilizet. In pigmented apphcations, calcium soaps, eg, calcium stearate, ate commonly used as internal lubricants to promote PVC fusion and reduce melt viscosity. This additive is also a powerfiil costabilizer for the alkyl tin mercaptide stabilizers at use levels of 0.2 to 0.7 phr. Calcium stearate can significantly improve the eady color and increase the long-term stabiUty at low levels however, as the concentration increases, significant yellowing begins to occur. 

Commercial Stabilizers. The performance of the antimony stabilizers is significantly enhanced by adding polyhydroxybenzene compounds, eg, catechol, to the PVC (36). In commercial practice, about 5—10% catechol is formulated with the antimony mercaptide stabilizer products. The antimony mercaptides are normally prepared by heating antimony oxide with the appropriate mercaptan, normally isooctyl thioglycolate, under conditions to remove water. 

The biochemical basis for the toxicity of mercury and mercury compounds results from its ability to form covalent bonds readily with sulfur. Prior to reaction with sulfur, however, the mercury must be metabolized to the divalent cation. When the sulfur is in the form of a sulfhydryl (— SH) group, divalent mercury replaces the hydrogen atom to form mercaptides, X—Hg— SR and Hg(SR)2, where X is an electronegative radical and R is protein (36). Sulfhydryl compounds are called mercaptans because of their ability to capture mercury. Even in low concentrations divalent mercury is capable of inactivating sulfhydryl enzymes and thus causes interference with cellular metaboHsm and function (31—34). Mercury also combines with other ligands of physiological importance such as phosphoryl, carboxyl, amide, and amine groups. It is unclear whether these latter interactions contribute to its toxicity (31,36). 

Pt(CO)2Cl2] is used to deposit thin films of metallic platinum on surfaces. Concentiated organic solutions of poorly defined platinum complexes of alkyl mercaptides or sulforesinates are used to coat ceramics and glass. 

An important aspect of this is the splitting of the polymer chain with thiol (eq. 5) or mercaptide ion (thiol + base catalyst). In fact, sodium sulfide or organic monothiols, eg, mercaptoethanol or decyhnercaptan, are utilized to lower the molecular weight of polysulftdes or to limit the extent of curing reactions. 

Solvent for Displacement Reactions. As the most polar of the common aprotic solvents, DMSO is a favored solvent for displacement reactions because of its high dielectric constant and because anions are less solvated in it (87). Rates for these reactions are sometimes a thousand times faster in DMSO than in alcohols. Suitable nucleophiles include acetyUde ion, alkoxide ion, hydroxide ion, azide ion, carbanions, carboxylate ions, cyanide ion, hahde ions, mercaptide ions, phenoxide ions, nitrite ions, and thiocyanate ions (31). Rates of displacement by amides or amines are also greater in DMSO than in alcohol or aqueous solutions. Dimethyl sulfoxide is used as the reaction solvent in the manufacture of high performance, polyaryl ether polymers by reaction of bis(4,4 -chlorophenyl) sulfone with the disodium salts of dihydroxyphenols, eg, bisphenol A or 4,4 -sulfonylbisphenol (88). These and related reactions are made more economical by efficient recycling of DMSO (89). Nucleophilic displacement of activated aromatic nitro groups with aryloxy anion in DMSO is a versatile and useful reaction for the synthesis of aromatic ethers and polyethers (90). 

Sulfur is reactive ia many forms. Mercaptides are alkylated to thioethers, and thioethers react further to give sulfonium salts, R2S" CH20S0 2-Suitable thiones also alkylate. Thioachdone (34) and thiourea (35) are examples the first gives the alkylmetcaptoacridine and the second gives the isothiourea. 

Dialkyl and diarylthaHium(III) derivatives are stable, crystalline soHds that melt at 180—300°C. The dimethylthaHium derivatives of CN , CIO, BF, and NO 2 contain linear (CH2)2T1 cations and the free anions (19). In aqueous solutions, they ionize to the (CH2)2T1(H20) ions, except those derivatives containing alkoxide, mercaptide, or amide anions, which yield dimeric stmctures (20,21). 

Mercaptides are unchallenged as the ligand of choice for the other entities bonded to the tin, but carboxylates can also be used. Whereas a variety of mercaptans are used, the thioglycolic acid derivatives remain the largest single mercaptan. Dibutyltin bis(isooctyl thioglycolate) [25168-24-5] and butyltin tris(isooctyl thioglycolate) [25852-70A] are two common examples. These materials are produced by the reaction of the appropriate alkyl tin chloride or oxide, and the mercaptan. 

Whereas other metal salts, especially lead stearates and srdfates, or mixtures of Groups 2 and 12 carboxylates (Ba—Cd, Ba—Zn, Ca—Zn) ate also used to stabilize PVC, the tin mercaptides are some of the most efficient materials. This increased efficiency is largely owing to the mercaptans. The principal mechanism of stabilization of PVC, in which all types of stabilizers participate, is the adsorption of HCl, which is released by the PVC during degradation. This is important because the acid is a catalyst for the degradation, thus, without neutralization the process is autocatalytic. 

Unlike other stabilizers, tin mercaptide, or the mercaptan that is formed after the HCl reacts with the mercaptide, can react with the allyhc chlorine to produce a sulfide (47), thus eliminating the labile chlorine groups and stopping the unzipping. 

The mercaptan or mercaptide can also add directiy to the olefin to break up or shorten the conjugation. 

Additionally, organotin mercaptides can act as antioxidants, as they can sequester free-radical degradation mechanisms (48). The one drawback of mercaptide-based tin stabilizers is the discoloration of the sulfur after exposure to uv-radiation. Special precautions or formulations need to be developed for outdoor apphcations. 

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