Rubbers, additives Vulcanisation accelerators

It is of interest to examine the development of the analytical toolbox for rubber deformulation over the last two decades and the role of emerging technologies (Table 2.9). Bayer technology (1981) for the qualitative and quantitative analysis of rubbers and elastomers consisted of a multitechnique approach comprising extraction (Soxhlet, DIN 53 553), wet chemistry (colour reactions, photometry), electrochemistry (polarography, conductometry), various forms of chromatography (PC, GC, off-line PyGC, TLC), spectroscopy (UV, IR, off-line PylR), and microscopy (OM, SEM, TEM, fluorescence) [10]. Reported applications concerned the identification of plasticisers, fatty acids, stabilisers, antioxidants, vulcanisation accelerators, free/total/bound sulfur, minerals and CB. Monsanto (1983) used direct-probe MS for in situ quantitative analysis of additives and rubber and made use of 31P NMR [69]. 

For the purpose of polymer/additive analysis most applications refer to vulcanisate analysis. Weber [370] has determined various vulcanisation accelerators (Vulkazit Thiuram/Pextra N/Merkapto/AZ/DM) in rubbers using PC. Similarly, Zijp [371] has described application of PC for identification of various vulcanisation accelerator classes (guanidines, dithiocarbaminates, thiuramsulfides, mercapto-substituted heterocyclic compounds, thioureas, etc.). The same author has also... 

Gorman [971] has described thermal desorption of volatile additives from rubber. The quantitative analysis of 2,2,4-trimethyl-1,2-dihydroquinoline (TMQ) in natural rubber by means of TD-GC-MS has been reported [1018a]. Off-line TD-GC-MS at 180°C of a 75/25 SBR/BR vulcanisate showed t-butylamine, CS2 and benzothiazole, indicative of the vulcanisation accelerator Vulkacit NZ (TBBS) [1019]. Analysis of seals for hydrocarbons and silicon-containing components by means of direct thermal desorption outperforms previous methods based on cyclohexane extraction and headspace techniques [1020]. 

Deformulation of vulcanised rubbers and rubber compounds at Dunlop (1988) is given in Scheme 2.3. Schnecko and Angerer [72] have reviewed the effectiveness of NMR, MS, TG and DSC for the analysis of rubber and rubber compounds containing curing agents, fillers, accelerators and other additives. PyGC has been widely used for the analysis of elastomers, e.g. in the determination of the vulcanisation mode (peroxide or sulfur) of natural rubbers. 

FAB has been used to analyse additives in (un) vulcanised elastomer systems [92,94] and FAB matrices have been developed which permit the direct analysis of mixtures of elastomer additives without chromatographic separation. The T-156 triblend vulcanised elastomer additives poly-TMDQ (AO), CTP (retarder), HPPD (antiozonant), and TMTD, OBTS, MBT and A,lV-diisopropyl-2-benzothiazylsulfenamide (accelerators) were studied in three matrix solutions (glycerol, oleic acid, and NPOE) [94]. The thiuram class of accelerators were least successful. Mixture analysis of complex rubber vulcanisates without chromatographic separation was demonstrated. The differentiation of matrix ions from sample ions was enhanced by use of high-resolution acquisition. 

Carbon disulphide reacts additively with primary and secondary aliphatic amines to form alkylammonium salts of alkyldithiocarbamic acids. The products obtained with dimethylamine, diethylamine and piperidine, also certain derivatives of these products, are manufactured on a large scale for use as accelerators in the vulcanisation of rubber. With aromatic amines the disulphide reacts with elimination of hydrogen sulphide and formation of substituted thio-ureas, e.g. thiocarbanilide. 

Most EPDM applications require crosslinking except when used as an impact modifier for PP, polystyrene (PS) and polyamides or as an oil additive, e.g., as viscosity index improver or dispersant. Most commonly, accelerated sulfur vulcanisation is used for the crosslinking of EPDM. As a result of the low amount of unsaturation in EPDM (< 1 mole/ kg versus NR -15 mole/kg), sulfur vulcanisation of EPDM is rather slow and a relatively large amount of accelerators is needed. Because of the low polarity of EPDM the solubility of polar accelerators is limited, often resulting in low effectivity and/or blooming. Typically, up to 5 different accelerators are used in EPDM formulations. As for other rubbers environmental issues, such as nitrosamine formation and may be in the future the presence of zinc, are prompting the development of new accelerator systems. 

In this chapter, some of these uses are explored in greater detail. Goodyear and Hancock in 1847 discovered that, when natural rubber was heated with a small amount of sulfur, the physical properties of the resultant rubber were improved the material became tougher and more resistant to changes in temperature. This process of vulcanisation is also useful for the treatment of synthetic rubbers, and as well as sulfur, many sulfur donors such as symmetrical diphenylthiourea, tetraalkylthiuram disulfides (1) and 2-mercaptobenzothia-zole (2) (Figure 1) can be used.1 These compounds act as accelerators of the process of polymerisation of the diene monomers in synthetic rubbers for this purpose, the additional presence of zinc oxide and preferably a carboxylic acid, e.g. stearic acid, is required. 

Rudewicz and Munson [45] used this technique for the direct determination of additives in PP. The technique has also been used to determine oligomers in polyacrylates, PEG, siloxanes and polycarbonates [87], polyglycols [88] and adhesion promoters, primers and additives in the surface of PET film [89], volatile antioxidants in styrene-butadiene rubbers [34, 50], mercaptobenzothiazole sulfenamide accelerator in rubber vulcanisates [90] and divinyl benzene in styrene-divinyl benzene copolymer [91]. 

In the compounding of rubber formulations, many types of additives are used, some of which, such as antiozonants, are not usually included in polymer formulations. One of the earliest and most comprehensive procedures for the examination of vulcanisates was published by Zijp [114] in 1956. He subjected extracts of the vulcanisates to various preliminary treatments after which the compounding ingredients or their residues were separated and identified using paper chromatography. Somewhat later, Gaczynski and Stephen [115] published a paper chromatographic method for the identification of the accelerators most commonly used in Poland at that time. 

It has been demonstrated previously that such additions can increase the strength of rubber-brass adhesion considerably. In this research it was established that polysulphides are only weak crosslinking agents for unsaturated rubber by themselves. In the presence of sulphenamide accelerators, such as OBTS, polysulphides, in amounts of 0.5 - 1 phr, activate the sulphur vulcanisation. However, the reversion process (crosslink breakdown) is not accelerated. A favourable effect on the physicomechanical properties of the vulcanisate was also reported. 

Oguri [970] has described the use of HS-GC in the analysis of additives in vulcanised rubbers and reinforcing materials. Accelerator fragments and AOs in vulcanised rubbers have been determined by SHS-GC-MS/FTIR/FID [971]. HS-GC is also used to determine volatile decomposition products of peroxide initiators in final resins. Tsuge et al. [972] have applied HS-GC to the determination of ester plasticisers and phenolic and amine AOs in a butadiene rubber. 

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