Rubber polymer identification

It is quite clear from Schemes 2.1-2.5 that in rubbers polymer identification and additive analysis are highly interlinked. This is at variance to procedures used in polymer/additive analysis. The methods for qualitative and quantitative analysis of the composition of rubber products are detailed in ASTM D 297 Rubber Products-Chemical Analysis [39]. 

ESR can equally be used for detection of radicals in masticated rubber their identification in relation to the chemical structure might be approached with specific techniques such as electron nuclear double resonance (ENDOR). ESR studies also contribute to the understanding of the char forming process of various polymers [815], to the study of mechanical fracture, which produces free radicals, grafting reactions, etc. Pedulli et al. [816,817] have determined the bond dissociation enthalpies of a-tocopherol and other phenolic AOs by means of ESR. The determination of the O—H bond dissociation enthalpies of phenolic molecules is of considerable practical interest since this class of chemical compounds includes most of the synthetic and naturally occurring antioxidants which exert their action via an initial hydrogen transfer reaction whose rate constant depends on the strength of the O—H bond. 

Polymer analysis is a major application of LD-FTMS. Laser desorption allows examination of materials that are otherwise difficult or impossible to study by mass spectrometric methods. For example, LD-FTMS and LD/EI-FTMS produce good results for hydrocarbon waxes, which are generally difficult to analyse. LDMS can be used to obtain information such as (i) degree of branching (ii) identification of monomers in copolymers (Hi) (Mw) (iv) MWD (as an alternative to SEC, MALDI-ToFMS and HTLC) and (v) in situ analysis of additives in polymers/rubbers without extensive sample pretreatment. LDMS is not most suited for on-line polymer identification, as separation of the polymer fragments requires time-consuming gas chromatography. 

This discussion of the structures of diene polymers would be incomplete without reference to the important contributions which have accrued from applications of the ozone degradation method. An important feature of the structure which lies beyond the province of spectral measurements, namely, the orientation of successive units in the chain, is amenable to elucidation by identification of the products of ozone cleavage. The early experiments of Harries on the determination of the structures of natural rubber, gutta-percha, and synthetic diene polymers through the use of this method are classics in polymer structure determination. On hydrolysis of the ozonide of natural rubber, perferably in the presence of hydrogen peroxide, carbon atoms which were doubly bonded prior to formation of the ozonide... 

Principles and Characteristics A first step in additive analysis is the identification of the matrix. In this respect the objective for most polymer analyses for R D purposes is merely the definition of the most appropriate extraction conditions (solvent choice), whereas in rubber or coatings analysis usually the simultaneous characterisation of the polymeric components and the additives is at stake. In fact, one of the most basic tests to carry out on a rubber sample is to determine the base polymer. Figure 2.1 shows the broad variety of additive containing polymeric matrices. 

Infrared spectroscopy is a major tool for polymer and rubber identification [11,12]. Infrared analysis usually suffices for identification of the plastic material provided absence of complications by interferences from heavy loadings of additives, such as pigments or fillers. As additives can impede the unambiguous assignment of a plastic, it is frequently necessary to separate the plastic from the additives. For example, heavily plasticised PVC may contain up to 60% of a plasticiser, which needs to be removed prior to attempted identification of the polymer. Also an ester plasticiser contained in a nitrile rubber may obscure identification of the polymer. Because typical rubber compounds only contain some 50% polymer direct FUR analysis rarely provides a definitive answer. It is usually necessary first... 

Alternative approaches consist in heat extraction by means of thermal analysis, thermal volatilisation and (laser) desorption techniques, or pyrolysis. In most cases mass spectrometric detection modes are used. Early MS work has focused on thermal desorption of the additives from the bulk polymer, followed by electron impact ionisation (El) [98,100], Cl [100,107] and field ionisation (FI) [100]. These methods are limited in that the polymer additives must be both stable and volatile at the higher temperatures, which is not always the case since many additives are thermally labile. More recently, soft ionisation methods have been applied to the analysis of additives from bulk polymeric material. These ionisation methods include FAB [100] and LD [97,108], which may provide qualitative information with minimal sample pretreatment. A comparison with FAB [97] has shown that LD Fourier transform ion cyclotron resonance (LD-FTTCR) is superior for polymer additive identification by giving less molecular ion fragmentation. While PyGC-MS is a much-used tool for the analysis of rubber compounds (both for the characterisation of the polymer and additives), as shown in Section 2.2, its usefulness for the in situ in-polymer additive analysis is equally acknowledged. 

Applications Shake-flask extraction nowadays finds only limited application in polymer/additive analysis. Carlson et al. [108] used this technique to extract antioxidants from rubber vulcanisates for identification purposes (NMR, IR, MS). Wrist-action shaking at room temperature was also used as the sample preparation step for the UV and IR determination of Ionol CP, Santonox R and oleamide extracted from pelletised polyethylene using different solvents [78]. BHT could be extracted in 98 % yield from powdered PP by shaking at room temperature for 30 min with carbon disulfide. 

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... 

Applications Conventional TLC was the most successful separation technique in the 1960s and early 1970s for identification of components in plastics. Amos [409] has published a comprehensive review on the use of TLC for various additive types (antioxidants, stabilisers, plasticisers, curing agents, antistatic agents, peroxides) in polymers and rubber vulcanisates (1973 status). More recently, Freitag [429] has reviewed TLC applications in additive analysis. TLC has been extensively applied to the determination of additives in polymer extracts [444,445]. 

In an acetone extract from a neoprene/SBR hose compound, Lattimer et al. [92] distinguished dioctylph-thalate (m/z 390), di(r-octyl)diphenylamine (m/z 393), 1,3,5-tris(3,5-di-f-butyl-4-hydroxybenzyl)-isocyanurate m/z 783), hydrocarbon oil and a paraffin wax (numerous molecular ions in the m/z range of 200-500) by means of FD-MS. Since cross-linked rubbers are insoluble, more complex extraction procedures must be carried out (Chapter 2). The method of Dinsmore and Smith [257], or a modification thereof, is normally used. Mass spectrometry (and other analytical techniques) is then used to characterise the various rubber fractions. The mass-spectral identification of numerous antioxidants (hindered phenols and aromatic amines, e.g. phenyl-/ -naphthyl-amine, 6-dodecyl-2,2,4-trimethyl-l,2-dihydroquinoline, butylated bisphenol-A, HPPD, poly-TMDQ, di-(t-octyl)diphenylamine) in rubber extracts by means of direct probe EI-MS with programmed heating, has been reported [252]. The main problem reported consisted of the numerous ions arising from hydrocarbon oil in the recipe. In older work, mass spectrometry has been used to qualitatively identify volatile AOs in sheet samples of SBR and rubber-type vulcanisates after extraction of the polymer with acetone [51,246]. 

LC-MS is now a nature technology and operation of an LC-MS system is no longer the realm of an MS specialist. The proper choice of the LC-MS mode to be used in a specific situation depends on analyte class, sample type and problem (detection, confirmation, identification). On-line LC-MS is used more for specialised applications than for general polymer or rubber compound analysis. This derives from the fact that LC-MS method development (column, solvent system, solvent programme, ionisation mode) is rather time consuming. LC-MS (in particular with API interface) enables analysis of a wide range of polar and nonvolatile compounds which cannot be analysed by GC (icf. Scheme 7.7). 

Applications Identification of polymer additives by TLC-IR is labour intensive and comprises extraction, concentration of extracts, component separation by TLC on silica, drying, removal of spots, preparation of KBr pellets and IR analysis. The method was illustrated with natural rubber formulations, where N-cyclohexyl-2-benzothiazyl sulfenamide, IPPD and 6PPD antioxidants, and a naphthenic plasticiser were readily quantified [765]. An overview of polymer/additive type compounds analysed by transfer TLC-FTIR is given in Table 7.80. 

The identification of chemical substances by examination of their spectra (singular, spectrum). Both infrared and ultraviolet spectroscopy are used in the study of rubber problems such as identifying the type of polymer or the nature of a contaminant. 

Gas chromatography (GC) and mass spectrometry (MS) can be coupled to the TGA instrument for online identification of the evolved gases during heating pyrolysis-GC/MS is a popular technique for the evaluation of the mechanism and the kinetics of thermal decomposition of polymers and rubbers. Moreover, it allows a reliable detection and (semi)quantitative analysis of volatile additives present in an unknown polymer sample. 

Analysts. Analytical investigations may be undertaken ro identify the presence of an ABS polymer, characterize the polymer, or identify nonpolymenc ingredients. Fourier transfrom infrared (fhr) spectroscopy is the method of choice to identify the presence of an ABS polymer and determine the acrylonitrile-butadiene-styrene ratio of the composite polymer. Confirmation of the presence of rubber domains is achieved by electron microscopy. Comparison with available physical properly data serves to increase confidence in the identification or indicate the presence of unexpected structural features. Phase-seperalion techniques can be used to provide detailed compositional analyses. 

Sircar [138] has reviewed the analysis of elastomer vulcanisate composition by TG/DTG techniques. The classical ASTM method, D297-93 [139], is too lengthy to be of much practical use on a routine basis, often requires preliminary identification of the polymer and is costly. TG has gained itself wide acceptance as a method for quantitative compositional analysis of vulcanisates ASTM El 131 [140], is basically designed for the analysis of rubber compounds [141]. Thermogravimetric analysis can be used to determine ... 

TG-FTIR Vulcanisation [32], ageing characterisation [39, 48], sulphur components in rubber [31], polyurethanes [37], polymer degradation mechanisms [30, 40, 41], identification of base polymers [36, 43, 44], thermal stability [46], grafted flame retardants [47], differentiation of EVA rubbers [45] and AN-NBR rubbers [36, 44], degradation of chlorinated natural rubber [42],... 

Some general applications of TG-FTIR are evolved gas analysis, identification of polymeric materials, additive analysis, determination of residual solvents, degradation of polymers, sulphur components from oil shale and rubber, contaminants in catalysts, hydrocarbons in source rock, nitrogen species from waste oil, aldehydes in wood and lignins, nicotine in tobacco and related products, moisture in pharmaceuticals, characterisation of minerals and coal, determination of kinetic parameters and solid fuel analysis. 

Schonherr [43] has described the combination of decomposition in a thermogravimetry oven and FTIR spectroscopy for the identification of base polymers in elastomers, as exemplified for nitrile rubber, and has presented infrared spectra for decomposition products of various rubbers. The same author [36] studied use of the integrated TG-FTIR system for the identification of sixteen vulcanised rubbers in mechanical goods reporting the characteristic infrared spectra of the degradation products at temperatures ranging from 334 °C to 635 °C. 

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