Polymer Extractables

Various workers have studied the use of HPLC-MS for the examination of polymer extractables [19-22]. Sidwell [20] of RAPRA Technology carried out a CC-MS and HPLC-MS study of the types of organosulfur compounds present in a range of rubber materials and other elastomers and the effect of ageing of various accelerators such as mercaptobenzothiazole on the migration of these compounds from rubbers in contact with foods. 

Barnes and co-workers [21] describe a HPLC-MS method for the determination of sulfur containing vulcanising agents in acidic acetonitrile extracts of foodstnffs which have been in contact with crosslinked rubbers. The detection limit was between 0.005 and 0.043 mg/kg for 2-mercaptobenzothiazole and benzothiazole. No trace of these two compounds and other vulcanising agents was found in any retail foodstuffs. 

Eberhardt and McCort-Tipton [23] have also applied HPLC-MS to the determination of species such as monomers, oligomers, additives and modifiers which have migrated from polymers into packaged foods. 

Barrett and co-workers [24] in their study of the thermal interaction between the sterically hindered phenolic antioxidant lonox 330 (1,3,5-trimethyl, 2,4,6 di- -butyl-4-hydroxy benzyl benzene) and the aromatic amine 4,4 -bis (a, a-dimethyl benzene) diphenyl amine showed by GC-MS over LC-MS that lonox 330 and its phenolic oxidation product stabilised either species. 

Vargo and Olsen [26] used MS detection in series with absorbance detection to identify or characterise antioxidants and UV-stabilising additives in acetonitrile extracts of PP, which were separated by LC. Nanogram quantities of additives could be detected. The procedure was used to characterise additives in PP samples of unknown composition. 

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Values in brackets indicate percentage of polymers extracted with acetone to total PVAc. 

The aim of this chapter is to summarize some of the research findings on xylan, a natural polymer extracted from corn cobs, which presents a promising application in the development of colon-specific drug carriers. Physicochemical characterization of the polymer regarding particle size and morphology, composition, rheology, thermal behavior, and crystallinity will be provided. Additionally, research data on its extraction and the development of microparticles based on xylan and prepared by different methods will also be presented and discussed. 

Several qualifying features for polymer extract analysis are summarised in Table 2.11. Quantitative separation of polymer and (thermolabile and/or volatile) additives without decomposition of the analyte(s) is difficult for thermoplasts, but even more difficult for... 

Recent attention has focused on MS for the direct analysis of polymer extracts, using soft ionisation sources to provide enhanced molecular ion signals and less fragment ions, thereby facilitating spectral interpretation. The direct MS analysis of polymer extracts has been accomplished using fast atom bombardment (FAB) [97,98], laser desorption (LD) [97,99], field desorption (FD) [100] and chemical ionisation (Cl) [100]. 

Conventional methods of polymer extraction use large quantities of solvents as in shake-flask extraction or a Soxhlet extraction apparatus. For all classical extraction methods, solvent selectivity, in general, is low, i.e. solvents with high capacity tend to have low selectivity. In reflux extractions, which are still quite popular in polymer applications, the polymer is refluxed with a hot solvent, which disperses it to provide a solvent phase containing additives. In these conditions solvents are at their atmospheric boiling point. These methods are lengthy and labour intensive. Fractional extraction is based on solvents with increasing solvent power (cf. also [81]). 

Desrosiers [23] considers ultrasonic bath extraction to be one of the best methods of in-polymer extraction. 

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]. 

By their nature, many UV absorbers are amenable to analysis by fluorimetric analysis. In many instances visible fluorescence techniques are less subject to interference by other polymer additives in a polymer extract than are UV methods of analysis. In fluorescence analysis (ex at 367 nm, em at 400-440 nm) of a PS/Uvitex OB chloroform dissolution AOs such as Ionol CP, Ionox 330, Polygard and Wingstay T/W do not interfere detection limit of 10 ppm [41]. 

Successful additive analysis on polymer extracts by means of 1-NMR generally means ... 

Many additives fragment quite extensively with FAB. The observation of molecular ion and many fragment ions for each additive makes the determination of the number of additives in the extract difficult if not impossible. Moreover, due to the matrix effect , not all the additives in polymer extracts are detected under FAB. 

Selection of a suitable ionisation method is important in the success of mixture analysis by MS/MS, as clearly shown by Chen and Her [23]. Ideally, only molecular ions should be produced for each of the compounds in the mixture. For this reason, the softest ionisation technique is often the best choice in the analysis of mixtures with MS/MS. In addition to softness , selectivity is an important factor in the selection of the ionisation technique. In polymer/additive analysis it is better to choose an ionisation technique which responds preferentially to the analytes over the matrix, because the polymer extract often consists of additives as well as a low-MW polymer matrix (oligomers). Few other reports deal with direct tandem MS analysis of extracts of polymer samples [229,231,232], DCI-MS/MS (B/E linked scan with CID) was used for direct analysis of polymer extracts and solids [69]. In comparison with FAB-MS, much less fragmentation was observed with DCI using NH3 as a reagent gas. The softness and lack of matrix effect make ammonia DCI a better ionisation technique than FAB for the analysis of additives directly from the extracts. Most likely due to higher collision energy, product ion mass spectra acquired with a double-focusing mass spectrometer provided more structural information than the spectra obtained with a triple quadrupole mass spectrometer. 

Also, direct determination of additives by means of laser desorption in solid polymeric materials rather than in polymer extracts has been reported [266], Takayama et al. [267] have described the direct detection of additives on the surface of LLDPE/(Chimassorb 944 LD and Irgafos P-EPQ) after matrix (THAP)-coating. As shown in Scheme 7.13, direct inlet mass spectrometry is also applicable to transfer TLC-MS and TLC-MS/MS analyses without the need for prior analysis. For direct sample introduction a small amount of the selected... 

Polymer extracts are frequently examined using GC-MS. Pierre and van Bree [257] have identified nonylphenol from the antioxidant TNPP, a hindered bisphenol antioxidant, the plasticiser DOP, and two peroxide catalyst residues (cumol and 2-phenyl-2-propanol) from an ABS terpolymer extract. Tetramethylsuccino-dinitrile (TMSDN) has been determined quantitatively using specific-ion GC-MS in extracts of polymers prepared using azobisisobutyronitrile TMSDN is highly volatile. Peroxides (e.g. benzoyl or lauroylperoxide) produce acids as residues which may be detected by MS by methylation of the evaporated extract prior to GC-MS examination [258]. GC-MS techniques are... 

In Chapter 5 it was argued that the prospects of multicomponent additive analysis of polymer extracts by means of UV and FTIR are not bright. Therefore, it should not be expected that this is improving for polymer/additive dissolutions. On the contrary, for such systems, essentially only NMR spectroscopy has led to significant results, although the number of pertinent reports is much restricted even here. 

HALS presents some analytical difficulties. Coulier et al. [18] describe a pyrolysis GC-MS method for identification and HPLC with UV and evaporative light scattering detection methods for quantification in polymer extracts. 

All these networks, B2, PCP2, and But 21-27, were stirred in benzene for 5 days and the uncrosslinked polymer extracted. 

Berglin M, Delage L, Potin P, Vilter H, Elwing H (2004) Enzymatic cross-linking of a phenolic polymer extracted from the marine algaFucus serratus. Biomacromolecules 5 2376-2383... 

Cl in conjunction with a direct exposure probe is known as desorption chemical ionization (DCI). [30,89,90] In DCI, the analyte is applied from solution or suspension to the outside of a thin resistively heated wire loop or coil. Then, the analyte is directly exposed to the reagent gas plasma while being rapidly heated at rates of several hundred °C s and to temperatures up to about 1500 °C (Chap. 5.3.2 and Fig. 5.16). The actual shape of the wire, the method how exactly the sample is applied to it, and the heating rate are of importance for the analytical result. [91,92] The rapid heating of the sample plays an important role in promoting molecular species rather than pyrolysis products. [93] A laser can be used to effect extremely fast evaporation from the probe prior to CL [94] In case of nonavailability of a dedicated DCI probe, a field emitter on a field desorption probe (Chap. 8) might serve as a replacement. [30,95] Different from desorption electron ionization (DEI), DCI plays an important role. [92] DCI can be employed to detect arsenic compounds present in the marine and terrestrial environment [96], to determine the sequence distribution of P-hydroxyalkanoate units in bacterial copolyesters [97], to identify additives in polymer extracts [98] and more. [99] Provided appropriate experimental setup, high resolution and accurate mass measurements can also be achieved in DCI mode. [100]... 

Normal-phase HPLC has been used increasingly during the past few years for the separation of PAs from grape seed and cocoa [11], PAs up to decamers were separated and resolved into equally spaced peaks in an order consistent with the degree of polymerization. However, for more complex polymers extracted from grape, the resolution becomes lower. 

Reclaim is a passive, in situ technology that uses a hydrophobic porous polymer to attract, adsorb, and concentrate petroleum hydrocarbons and volatile organic compounds (VOCs) from soils and/or groundwater. Reclaim is considered a passive treatment technology because it requires no mechanical equipment remediation consists of placing polymer-filled canisters in recovery wells and allowing the containers to attract and adsorb organic contaminants. Reclaim canisters are then recycled and contaminants recovered for analysis and/or disposal. This polymer extracts contaminants whether they are in liquid phase, vapor phase or dissolved phase in water. 

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