Antistatic agents, analysis

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]. 

Phenolic antioxidants in rubber extracts were determined indirectly photometrically after reaction with Fe(III) salts which form a red Fe(II)-dipyridyl compound. The method was applicable to Vulkanox BKF and Vulkanox KB [52]. Similarly, aromatic amines (Vulkanox PBN, 4020, DDA, 4010 NA) were determined photometrically after coupling with Echtrotsalz GG (4-nitrobenzdiazonium fluoroborate). For qualitative analysis of vulcanisation accelerators in extracts of rubbers and elastomers colour reactions with dithio-carbamates (for Vulkacit P, ZP, L, LDA, LDB, WL), thiuram derivatives (for Vulkacit I), zinc 2-mercaptobenzthiazol (for Vulkacit ZM, DM, F, AZ, CZ, MOZ, DZ) and hexamethylene tetramine (for Vulkacit H30), were mentioned as well as PC and TLC analyses (according to DIN 53622) followed by IR identification [52]. 8-Hydroquinoline extraction of interference ions and alizarin-La3+ complexation were utilised for the spectrophotometric determination of fluorine in silica used as an antistatic agent in PE [74], Also Polygard (trisnonylphenylphosphite) in styrene-butadienes has been determined by colorimetric methods [75,76], Most procedures are fairly dated for more detailed descriptions see references [25,42,44],... 

Dobanol Ethoxy late [443], At least 16 Triton units with mass 910 were observed. A study of the reactions of amines and amine derivatives with scC02 using cSFC-MS was also reported [448], Both cSFC-APCI-MS and cSFC-ESI-MS of PEG 600 and PPG 425 were described [416]. Direct insertion probe (DIP) methodology was used for the structure analysis of the antistatic agent V,fV-bis-(2-hydroxyethyl)alkylamine. When analysed by SFC-MS coupling, the same sample could be separated into six components. The alkyl chains consist of saturated Cn, Ci4, C16 and C18 chains and of Cig chains with one double bond where 18 1 and 16 0 chains dominate. 

Blowing agents include azodicarbonamide, azodiisobutyronitrile, etc. Antistatic agents include quaternary ammonium compounds, etc. With the added complexity due to the presence of these compounds, the analysis of polymeric blends and of practical objects made from polymers containing additives is not always simple. 

It is necessary to be able to identify and quantify the additives in polymers and vibrational spectroscopy is a particularly useful approach to this problem. Compared with traditional chemical analyses, vibrational methods are nondestructive and are time-and cost-effective as well as more precise. A large number of examples exist in the literature. For example, antistatic agents (polyethylene glycol (PEG) in polyethylene (PE)) can be detected directly using FTIR sampling (367). An IR spectroscopic technique for the analysis of stabilisers (2, 6-di-tert-butyM-methylphenol) in PE and ethylene-vinyl acetate (EVA) copolymer has been described (368). It is possible to quantify the amount of external and internal lubricants (stearic acid in polystyrene (PS)) (371). Fillers in polymers can also be analysed (white rice husk ash (predominantly silica in polypropylene (PP)) (268). Raman spectroscopy has been used to detect residual monomer in solid polymethyl methacrylate (PMMA) samples (326). 

The complete analysis of a commercial polymer provides an interesting challenge since the materials are rarely, if ever, pure components so the identification and quantitative evaluation of the base polymer is part of a much wider investigation. In order to enhance the processing or physical properties of the materials, many additives are deliberately introduced. Typically, these might include antioxidants, antistatic agents, pigments, fire retardants, plastisizers and many more (see Table 2.1). 

The selection of an antistatic agent depends greatly on the polymer matrix since a degree of incompatibility is vital to ensure that migration to the surface of the product occurs at a fast rate after manufacture. Exact chemical composition information can be difficult to obtain from suppliers and so analysis for these additives can be difficult. 

Chem. Descrip. Fatty amine oxide Chem. Analysis 0.3% max.free amine 0.03% max. free HjOj Uses Stabilizer, vise, increases emollient, detergent antistat agent in many detergents, shampoos and conditioners Features Mild to skin... 

David et al. [184] have shown that cool on-column injection and the use of deactivated thermally stable columns in CGC-FID and CGC-F1D-MS for quantitative determination of additives (antistatics, antifogging agents, UV and light stabilisers, antioxidants, etc.) in mixtures prevents thermal degradation of high-MW compounds. Perkins et al. [101] have reported development of an analysis method for 100 ppm polymer additives in a 500 p,L SEC fraction in DCM by means of at-column GC (total elution time 27 min repeatability 3-7 %). Requirements for the method were (i) on-line (ii) use of whole fraction (LVI) and (iii) determination of high-MW compounds (1200 Da) at low concentrations. Difficult matrix introduction (DMI) and selective extraction can be used for GC analysis of silicone oil contamination in paints and other complex analytical problems. 

Hunt et al. [354] used cSFC for the separation of extracts of poly(alkylene glycol) lubricants and sorbitan ester formulations. Doehl et al. [337] have compared the performance of cSFC-FID and pSFC-FID with both scC02 and scN20 in the analysis of the antiblocking agents oleamide and erucamide, the antistatic Armostat 400 and antioxidant Hostanox SE-10, none of which can be detected by UV absorption. By using open-tubular capillary columns, PAs as well as (un)substituted heavy carboxylic acids (> C ) can be eluted. 

U V fluorescent sulfur detection and chemiluminescent nitrogen methods have been developed for total sulfur only, nitrogen only or simultaneous sul-fur/nitrogen analysis. These systems provide quick automated analysis to estimate the type and amount of sulfur and nitrogen-containing additives present in a polyolefin sample, i.e. slip agents, antistatics. 

---