Plasticisers determinations

This technique is extremely useful. For example, it has been used to identify and determine plasticisers in PVC and antioxidants in PE. 

Methods have been described for determining plasticisers in a variety of foodstuffs, milk, cheese and butter. 

The minimum service temperature is determined primarily by the Tg of the soft phase component. Thus the SBS materials ctm be used down towards the Tg of the polybutadiene phase, approaching -100°C. Where polyethers have been used as the soft phase in polyurethane, polyamide or polyester, the soft phase Tg is about -60°C, whilst the polyester polyurethanes will typically be limited to a minimum temperature of about 0°C. The thermoplastic polyolefin rubbers, using ethylene-propylene materials for the soft phase, have similar minimum temperatures to the polyether-based polymers. Such minimum temperatures can also be affected by the presence of plasticisers, including mineral oils, and by resins if these become incorporated into the soft phase. It should, perhaps, be added that if the polymer component of the soft phase was crystallisable, then the higher would also affect the minimum service temperature, this depending on the level of crystallinity. 

More recently, the same author [41] has described polymer analysis (polymer microstructure, copolymer composition, molecular weight distribution, functional groups, fractionation) together with polymer/additive analysis (separation of polymer and additives, identification of additives, volatiles and catalyst residues) the monograph provides a single source of information on polymer/additive analysis techniques up to 1980. Crompton described practical analytical methods for the determination of classes of additives (by functionality antioxidants, stabilisers, antiozonants, plasticisers, pigments, flame retardants, accelerators, etc.). Mitchell... 

In the rubber field it is not only the polymer that determines the properties of an elastomer, but many accompanying substances, like fillers, pigments, plasticisers, curing agents, antioxidants, stabilisers and processing aids (cf. Table 2.2). With rubbers the possible compositional permutations are numerous. In fact, already within the additive group of CBs there are more than 30 different possible products. 

Plasticiser/oil in rubber is usually determined by solvent extraction (ISO 1407) and FTIR identification [57] TGA can usually provide good quantifications of plasticiser contents. Antidegradants in rubber compounds may be determined by HS-GC-MS for volatile species (e.g. BHT, IPPD), but usually solvent extraction is required, followed by GC-MS, HPLC, UV or DP-MS analysis. Since cross-linked rubbers are insoluble, more complex extraction procedures must be carried out. The determination of antioxidants in rubbers by means of HPLC and TLC has been reviewed [58], The TLC technique for antidegradants in rubbers is described in ASTM D 3156 and ISO 4645.2 (1984). Direct probe EIMS was also used to analyse antioxidants (hindered phenols and aromatic amines) in rubber extracts [59]. ISO 11089 (1997) deals with the determination of /V-phenyl-/9-naphthylamine and poly-2,2,4-trimethyl-1,2-dihydroquinoline (TMDQ) as well as other generic types of antiozonants such as IV-alkyl-AL-phenyl-p-phenylenediamines (e.g. IPPD and 6PPD) and A-aryl-AL-aryl-p-phenylenediamines (e.g. DPPD), by means of HPLC. 

In extraction from a polymer/additive solid matrix the rate-determining step in the extraction process is governed by the interaction of the solvent of sufficient dissolution power with the matrix and the removal of the analyte (cf. Section 3.4.1.3). There appears to exist a direct relationship between degree of swelling and efficiency of extraction. The amount of C02 absorbed depends on temperature, pressure and the polymer concerned. Crystalline polymers are-not surprisingly-plasticised less... 

Some typical applications in SFE of polymer/additive analysis are illustrated below. Hunt et al. [333] found that supercritical extraction of DIOP and Topanol CA from ground PVC increased with temperature up to 90 °C at 45 MPa, then levelled off, presumably as solubility became the limiting factor. The extraction of DOP and DBP plasticisers from PVC by scC02 at 52 MPa increased from 50 to 80 °C, when extraction was almost complete in 25 min [336]. At 70 °C the amount extracted increased from 79 to 95 % for pressures from 22 to 60 MPa. SFE has the potential to shorten extraction times for traces (<20ppm) of additives (DBP and DOP) in flexible PVC formulations with similar or even better extraction efficiencies compared with traditional LSE techniques [384]. Marin et al. [336] have used off-line SFE-GC to determine the detection limits for DBP and DOP in flexible PVC. The method developed was compared with Soxhlet liquid extraction. At such low additive concentrations a maximum efficiency in the extractive process and an adequate separative system are needed to avoid interferences with other components that are present at high concentrations in the PVC formulations, such as DINP. Results obtained... 

SPE has been applied to phthalate esters (plasticisers in PVC), polar pesticides (agricultural usage) and for other continuous pollution monitoring problems and environmental analyses [272]. For these applications SPE has largely displaced LLE as the preferred technique for the preparation of liquid samples, e.g. EPA method 506 is concerned with the determination of phthalates and adipate esters in drinking water. 

SPME-IR has been applied to VOCs in soil samples [547], Industrial applications to in-process streams can well be envisaged. SPME has not yet extensively been explored for polymers, but the determination of residual volatiles, semi-volatiles and degradation products in polymers has been reported [548]. It is equally well possible to use SPME for plasticiser analysis in various matrices (water, milk, blood, processed food, etc.). 

Gas chromatography is widely applied in the paint and varnish industry for analysis of solvents, oils, resins, plasticisers and polymers (by pyrolysis techniques). GC-TCD and GC-FTD on capillary and packed columns are used for direct determination of solvents in paints [143,144], DIN ISO 11890-2 describes an officially approved GC test procedure for solvents in paints and varnishes (VOCs 0.1-15%). 

GC is equally useful in the determination of the transfer of plasticisers from polymers to food products... 

Cyclic oligomers of PA6 can be separated by PC [385,386] also PET and linear PET oligomers were separated by this technique [387]. Similarly, PC has been used for the determination of PEGs, but was limited by its insensitivity and low repeatability [388]. PC was also used in the determination of Cd, Pb and Zn salts of fatty acids [389]. ATR-IR has been used to identify the plasticisers DEHP and TEHTM separated by PC [390]. Although this combined method is inferior in sensitivity and resolution to modem hyphenated separation systems it is simple, cheap and suitable for routine analysis of components like polymer additives. However, the applicability of ATR-IR for in situ identification of components separated by PC is severely restricted by background interference. 

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]. 

As the majority of stabilisers has the structure of aromatics, which are UV-active and show a distinct UV spectrum, UV spectrophotometry is a very efficient analytical method for qualitative and quantitative analysis of stabilisers and similar substances in polymers. For UV absorbers, UV detection (before and after chromatographic separation) is an appropriate analytical tool. Haslam et al. [30] have used UV spectroscopy for the quantitative determination of UVAs (methyl salicylate, phenyl salicylate, DHB, stilbene and resorcinol monobenzoate) and plasticisers (DBP) in PMMA and methyl methacrylate-ethyl acrylate copolymers. From the intensity ratio... 

For direct determination of plasticisers in PVC the sample was dissolved in THF, and phthalate or phosphate plasticisers were measured from absorbance at 240 and 275 nm or 257, 262 and 268 nm, respectively... 

On-line SFE-GC finds use especially in petroleum-related applications [54], but has also been applied to polymer additives [47,55]. PBT polymers were extracted at 200 bar and 55 °C for the determination of carbonic acid diphenyl esters and other volatiles, using on-line SFE-GC-MS [47]. Extraction of entrained volatiles is a quality test for some polymers. SFE-GC-FTIR-MS has been employed to reveal the cause of odour of a smelly hose (a plasticiser) [56]. SFE-GC can also profitably be used for the determination of residual solvents in polymers such as benzene, toluene and o-xylene [57]. Oligomers of PE (up to 1000 Da) were determined by GC after supercritical fluid extraction [58]. 

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