Flame retardants, analysis

Pijnenburg, A., Everts, J., and de Boer, J. et al. (1995). Polybrominated biphenyl and diphe-nylether flame retardants analysis, toxicity, and environmental occurrence. Reviews in Environmental Contamination and Toxicology. 141, 1-26. 

Pijnenburg AMCM, Everts JW.de Boer J, Boon JP (1995) Polybrominated biphenyl and diphenyl ether flame retardants analysis, toxicity, and environmental occurrence. In Ware GW (ed) Reviews of environmental contamination and toxicology, vol 141. Springer, Berlin Heidelberg New York, p 2... 

Laboratory experiments using rodents, or the use of gas analysis, tend to be confused by the dominant variable of fuel—air ratio as well as important effects of burning configuration, heat input, equipment design, and toxicity criteria used, ie, death vs incapacitation, time to death, lethal concentration, etc (154,155). Some comparisons of polyurethane foam combustion toxicity with and without phosphoms flame retardants show no consistent positive or negative effect. Moreover, data from small-scale tests have doubtful relevance to real fine ha2ards. 

M. Freiberg, D.L. McAllister, C.J. Mazac, P. Ranken Analysis of Trace Levels of Polybrominated Dibenzo-p-dioxins and Dibenzofurans in Brominated Flame Retardants Presented on June 30, 1993 at Orgabrom 93 in Jerusalem. 

ICI Acrylics believes that greater cooperation between companies and a revised approach to life cycle analysis are the keys to the industry s future environmental sustainability. The company has invested over 2m pounds sterling in an on-going monomer recovery project, which encompasses a joint research programme with Mitsubishi Rayon. The project focuses on increasing the efficiency of acrylic depolymerisation and overcoming technical issues such as its use in recycling flame retardant acrylics. ICI ACRYLICS... 

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... 

Applications The method is in use for the determination of water extractable organics in PA6 and PA4.6, and for alkane extraction of waxes from HDPE (in nitrogen atmosphere to prevent oxidation) [156]. Ethylene-bis-stearamide (EBA) can be extracted from ABS in 30 min using intermittent extraction in this case quantitative Soxhlet extraction was not possible. Nelissen [157] has used intermittent extraction with MTBE for the analysis of the flame retarder system of Tribit 1500 GN30. 

Brandt [200] has extracted tri(nonylphenyl) phosphite (TNPP) from a styrene-butadiene polymer using iso-octane. Brown [211] has reported US extraction of acrylic acid monomer from polyacrylates. Ultrasonication was also shown to be a fast and efficient extraction method for organophosphate ester flame retardants and plasticisers [212]. Greenpeace [213] has recently reported the concentration of phthalate esters in 72 toys (mostly made in China) using shaking and sonication extraction methods. Extraction and analytical procedures were carefully quality controlled. QC procedures and acceptance criteria were based on USEPA method 606 for the analysis of phthalates in water samples [214]. Extraction efficiency was tested by spiking blank matrix and by standard addition to phthalate-containing samples. For removal of fatty acids from the surface of EVA pellets a lmin ultrasonic bath treatment in isopropanol is sufficient [215]. It has been noticed that the experimental ultrasonic extraction conditions are often ill defined and do not allow independent verification. 

Various techniques have been used for the determination of oligomers, including GC [135], HPLC [136-138], TLC for polystyrene and poly a-methyl-styrene [139] and SEC for polyesters [140,141]. GC and PyGC-MS can also profitably be used for the analysis of the compositions of volatile products formed using different flame retardants (FRs). Takeda [142] reported that volumes and compositions of the volatile products and morphology of the char were affected by FRs, polymers (PC, PPE, PBT) and their reactions from 300... 

CE is also potentially a useful alternative analytical tool for monitoring of chemicals (dyes, flame retardants and lubricants) involved in various steps of the textile fibre manufacturing process. In this area, CE compares favourably with existing techniques. CZE-MSn was used for the analysis of sulfonated azo dyes [942]. A variety of fluorescent analytes including thiazole orange dyes have been characterised by CE-FLNS [943]. 

Direct pyrolysis in the ion source of a mass spectrometer (QMS) was used to analyse PE/(dicumylperoxide, Santonox R) and PVC/DIOP [259]. In-source PyMS is an analytical tool for fast analysis of flame retardants in unknown mixtures of polymers [223, 265], Heeren and Boon [224] used in-source filament pyrolysis FTMS for high-speed, broadband screening of additives in polymeric household appliances. 

Flame retardants in polyurethane foams were determined by SFE-SFC [117]. Off-line SFE-SFC-FID was used for the analysis of additives in polyurethanes [52], and on-line SFE-SFC for extraction of additives from isocyanate formulations [107]. 

On-line SFE-GC-MS was used for the analysis of organic extractables from human hair [312]. Van Lieshout et al. [313] described GC-MS analysis of an SFE extract of an (ABS) impact-modified PC/PBT blend identifying Ionol CP, Dressinate, cyclic PBT trimer, Irganox 1076 and Irganox PS 800. TD-GC-MS was used in the development of flame retardants, and for the analysis of fire debris [314]. The application of laser desorption fast GC-MS analysis was employed in the analysis of DOP on a stainless-steel surface [221]. 

Successful combination of a chromatographic procedure for separating and isolating additive components with an on-line method for obtaining the IR spectrum enables detailed compositional and structural information to be obtained in a relatively short time frame, as shown in the case of additives in PP [501], and of a plasticiser (DEHP) and an aromatic phenyl phosphate flame retardant in a PVC fabric [502], RPLC-TSP-FTIR with diffuse reflectance detection has been used for dye analysis [512], The HPLC-separated components were deposited as a series of concentrated spots on a moving tape. HPLC-TSP-FTIR has analysed polystyrene samples [513,514], The LC Transform has also been employed for the identification of a stain in carpet yarn [515] and a contaminant in a multiwire cable [516], HPLC-FTIR can be used to maintain consistency of raw materials or to characterise a performance difference. 

Principles and Characteristics Combustion analysis is used primarily to determine C, H, N, O, S, P, and halogens in a variety of organic and inorganic materials (gas, liquid or solid) at trace to per cent level, e.g. for the determination of organic-bound halogens in epoxy moulding resins, halogenated hydrocarbons, brominated resins, phosphorous in flame-retardant materials, etc. Sample quantities are dependent upon the concentration level of the analyte. A precise assay can usually be obtained with a few mg of material. Combustions are performed under controlled conditions, usually in the presence of catalysts. Oxidative combustions are most common. The element of interest is converted into a reaction product, which is then determined by techniques such as GC, IC, ion-selective electrode, titrime-try, or colorimetric measurement. Various combustion techniques are commonly used. 

Houben [256] has compared the determination of flame-retardant elements Br, P, S, K, Cl and F in polycarbonate using commercial (X40 and UniQuant ) software. For the X40 method, a calibration line for each element in PC or PC/ABS blends was mapped for the conversion of intensities to concentrations. With the universal UniQuant method, sensitivity factors (ks) were calibrated with pure standards. The X40 method turned out to be more reliable than UniQuant for the determination of FRs in PC and PC/ABS blends, even in the case of calibration of k values with PC standards. Standard errors of 5 % were achieved for Br, P, S and K, and 20% for Cl and F the latter element could not be determined by means of UniQuant (Table 8.44). GFR PC cannot be quantified with these two methods, because of the heterogeneous nature of the composites. Other difficult matrices for XRF analysis are PBT, PS and PP compounds containing both BFRs and Sb203 (10-30wt %) due to self-absorption of Sb and interelement effects. 

Applications The general applications of XRD comprise routine phase identification, quantitative analysis, compositional studies of crystalline solid compounds, texture and residual stress analysis, high-and low-temperature studies, low-angle analysis, films, etc. Single-crystal X-ray diffraction has been used for detailed structural analysis of many pure polymer additives (antioxidants, flame retardants, plasticisers, fillers, pigments and dyes, etc.) and for conformational analysis. A variety of analytical techniques are used to identify and classify different crystal polymorphs, notably XRD, microscopy, DSC, FTIR and NIRS. A comprehensive review of the analytical techniques employed for the analysis of polymorphs has been compiled [324]. The Rietveld method has been used to model a mineral-filled PPS compound [325]. 

Covaci A, Harrad S, Abdallah MAE, Ali N, Law RJ, Herzke D, de Wit CA (2011) Novel brominated flame retardants a review of their analysis, environmental fate and behaviour. 

Illustrative Cost-Benefit Analysis of Flame Retardants in Furniture. 131... 

Keywords Brominated flame retardants, E-waste, Substance Flow Analysis SFA, Informal Recycling, Waste Electric and Electronic Equipment WEEE... 

Tasaki T, Takasuga T, Osako M, Sakai S-i (2004) Substance flow analysis of brominated flame retardants and related compounds in waste TV sets in Japan. Waste Manag 24(6) 571-580... 

Recently, several reports of the flame-retardant properties of boron-containing bisphenol-A resins have appeared from Gao and Liu.89 The synthesis of a boron-containing bisphenol-A formaldehyde resin (64 and 65) (Fig. 42) from a mixture of bisphenol-A, formaldehyde, and boric acid, in the mole ratio 1 2.4 0.5, has been reported.893 The kinetics of the thermal degradation and thermal stability of the resins were determined by thermal analysis. The analysis revealed that the resin had higher heat resistance and oxidative resistance than most common phenol-formaldehyde resins. 

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