Additives extraction

Suppose we have a sample containing an analyte in a matrix that is incompatible with our analytical method. To determine the analyte s concentration we first separate it from the matrix using, for example, a liquid-liquid extraction. If there are additional analytes, we may need to use additional extractions to isolate them from the analyte s matrix. For a complex mixture of analytes this quickly becomes a tedious process. 

M-iscellaneousFxtractions. Additional extractive separations using sulfolane involve (/) mercaptans and sulfides from sour petroleum (45) (2) /-butylstyrene from /-butylethjlbenzene (46) (J) mixtures of close boiling chlorosHanes (47) and (4) aromatics from kerosene (48—50), naphtha (49,51—53), and aviation turbine fuel (54). 

A number of antioxidants have been accepted by the FDA as indirect additives for polymers used in food appHcations. Acceptance is deterrnined by subchronic or chronic toxicity in more than one animal species and by the concentration expected in the diet, based on the amount of the additive extracted from the polymer by typical foods or solvents that simulate food in their extractive effects. Only materials of insignificant risk to the consumer are regulated by the FDA for use in plastics contacted by food stuffs. 

Another point is related to the high acidity level of the final solution, which leads to certain limitations in the subsequent technological steps. Specifically, the high acidity of the initial solution eliminates any possibility for selective extraction, i.e. sequential separation of tantalum and then of niobium. Due to the high concentration of acids, only collective extraction (of tantalum and niobium together) can be performed, at least at the first step. In addition, extraction from a highly acidic solution might cause additional contamination of the final products with antimony and other related impurities. In order to reduce the level of contaminants in the initial solution, some special additives are applied prior to the liquid-liquid extraction. For instance, some mineral acids and base metals are added to the solution at certain temperatures to cause the precipitation of antimony [455 - 457]. 

Following the same procedures described in the above-mentioned study, additional extractive data were obtained for the epoxy phenolic enamel that was irradiated at 4.7-7.1 Mrad at 25 and — 30 °C in the presence of distilled water, 3% acetic acid, and n-heptane. The changes in the amount of extractives resulting from the irradiation treatment are shown in Table IX. In the case of the water and acetic acid extractives, there was no change in either the chloroform-soluble fractions or the chloroform-insoluble fractions. In the case of the n-heptane extractives, the amount of extractives decreased when the irradiation temperature was reduced from +25 to — 30°C. Infrared spectra of the chloroform-soluble residues from the water and acetic acid extractives of the unirradiated and irradiated enamel were identical to the chloroform-soluble residues from the solvent blanks. In other words, the epoxy phenolic... 

Tea can be consumed directly either by brewing loose leaves or tea bags or in a ready-to-drink form. In addition, extracts of tea (primarily green tea) may be prepared in a variety of physical forms in order to cover most application requirements. 

A normal-phase HPLC separation seems to be useful to separate major chlorophyll derivatives, but it is not compatible with samples in water-containing solvents an additional extraction step is required to eliminate water from the extract since its presence rednces chromatographic resolution and interferes with retention times. Besides that, the analysis cannot be considered quantitative due to the difhculty in transferring componnds from the acetone solution into the ether phase. On the other hand, an advantage of the normal-phase method is its efficacy to separate magne-sinm-chlorophyll chelates from other metal-chelated chlorophyll derivatives. ... 

Micro reactors permit high-throughput screening of process chemistries imder controlled conditions, unlike most conventional macroscopic systems [2], In addition, extraction of kinetic parameters from sensor data is possible, as heat and mass transfer can be fully characterized due to the laminar-flow condihons applied. More uniform thermal condihons can also be utilized. Further, reactor designs can be developed in this way that have specific research and development funchons. 

Extraction procedure Sample Solvents for additive extraction and PP oligomer precipitation Time (h)... 

SFE has now been available long enough to allow an evaluation of its prospects for polymer/additive extraction. SFE is still around, but EPA and FDA approved SFE methods are still wanting. The main problem is strong matrix effects. SFE is not a cookbook method for one s matrix. Not unlike microwave extraction, SFE requires that a specific method be developed to optimise the recovery for each polymer/additive system. Therefore, the success of SFE depends on the polymer... 

A common technique used for polyolefin samples is to dissolve the sample using solvents such as xylene, decalin, toluene and di- or trichlorobenzene heated to temperatures as high as 130-150°C. After the plastic sample has been solvated, the polymeric component is precipitated by cooling and/or by adding a cold nonsolvent such as acetone, methanol or isopropanol. Polypropylene does not completely dissolve in toluene under reflux for 0.5 to 1 h with magnetic stirring (typically, 2g of polymer in 40 mL of toluene), yet the additives may be extracted [603]. In addition to additives, most solvents also extract some low-MW polymer with subsequent contamination of the extract. To overcome this a procedure for obtaining polymer-free additive extracts from PE, PP and PS has been described based on low-temperature extraction with n-hexane at 0°C [100],... 

Major applications of modern TLC comprise various sample types biomedical, pharmaceutical, forensic, clinical, biological, environmental and industrial (product uniformity, impurity determination, surfactants, synthetic dyes) the technique is also frequently used in food science (some 10% of published papers) [446], Although polymer/additive analysis takes up a small share, it is apparent from deformulation schemes presented in Chapter 2 that (HP)TLC plays an appreciable role in industrial problem solving even though this is not reflected in a flood of scientific papers. TLC is not only useful for polymer additive extracts but in particular for direct separations based on dissolutions. 

In SEC analysis of additive extracts from polymers, the effect of the extraction solvent on the mobile phase is less critical than in HPLC analysis. The extraction solvents typically employed generally do not interfere with the SEC mobile phases. Moreover, the same solvents are often used both as extraction solvent and as mobile phase. Therefore, there is no need to evaporate the extract to dryness prior to analysis and then to redissolve it in a suitable solvent. Typical extraction procedures often produce extracts that generally contain a small amount of wax. Frequently, removal of such oligomers from an extract is necessary, e.g. by means of precipitation, centrifuging, precolumn filtration or protection (use of a reversed-phase guard column). In SEC separations the presence of polyolefin wax does not usually disturb provided that the MW of the wax is higher than that of the analysed compounds. 

Table 5.9 Main characteristics of FTIR spectroscopy for polymer/additive extracts...

In conclusion, IR analysis of polymer/additive extracts before chromatographic separation takes advantage mainly of straightforward transmission measurements. Without separation it is often possible to make class assignments (e.g. in the reported examples on plasticisers and carbodiimide hydrolysis stabilisers) it may eventually be necessary to use multivariate techniques. Infrared detection of chromatographic effluents is dealt with in Chapter 7. 

Instrumentation for fluorescence spectroscopy has been reviewed [8]. For standards in fluorescence spectroscopy, see Miller [138]. Fluorescence detection in HPLC has recently been reviewed [137], Phosphorescence detection of polymer/additive extracts is not being practised. 

Nowadays, MS is often no longer the analytical bottleneck, but rather what precedes it (sample preparation) and follows it (data handling, searching). Direct mass-spectrometric methods have to compete with the separation techniques such as GC, HPLC and SFC that are commonly used for quantitative analysis of polymer additives. Extract analysis has the general advantage that higher-molecular-weight (less-volatile) additives can be detected more readily than by direct analysis of the polymer compound. 

C, is one of the most critical parameters in TSP operation, and should be optimised for different samples, wherever possible. This is considered to be a considerable drawback in routine operation of unknown polymer/additive extracts. Too low a vaporiser temperature results in the solute and solvent spraying into the ionisation source in their liquid form, without formation of gas-phase ions. Too high a vaporiser temperature causes premature evaporation of the solute and solvent before the outlet of the capillary is reached. This causes an unstable, pulsing ion beam. As ion formation in TSP operation depends very critically on the extent of desolvation and the energy of the nebulised droplets, it is clear that an inappropriate vaporiser temperature will cause loss of sensitivity. 

Figure 7.29 LC-PB-MS retention time-mass plot of a polymer additive extract. Courtesy of F. Ploeg, Waters/Micromass, Etten-Leur. Reproduced by permission of Waters Corporation...

Various LC-PB-MS and LC-APCI-MS comparisons have been reported on polymer additive extracts [540, 563,629,630]. The complementary character of the El and APCI modes was confirmed. Yu et al. [630] compared LC-PB-MS and RPLC-UV-APCI-MS for detection and identification of unknown additives (in the 252 to 696 Da range) in an acetonitrile extract from PP (containing Irganox 1076, Naugard XL-1 and a degradation product, NC-4, 3-(3,5-di-f-butyl-4-hydroxyphenyl) propanoic acid, 7,9-di-f-butyl-l-oxaspiro [4,5] deca-6,9-diene-2,8-dione and octadecanol-1). Comparison was based on El data (identification of chemical structure), APCI (MW information CID spectrum with limited fragmentation) and PDA (210 nm). The components were identified by El and confirmed by APCI- (with better sensitivity and linearity) MS and PDA showed... 

Requirements for 1-NMR analysis of a polymer/additive solute are essentially the same as for additive extracts, namely ... 

Mass analysis of polymer/additive extracts (i.e. without the polymeric component, see Chapter 6) is obviously... 

Desorption chemical ionisation (DCI) mass spectrometry has been used for detecting additives extracted from polymers [51,52] by a solvent as volatile as possible. To use the DCI probe, 1 -2 iL of the sample, in solution, are applied to the probe tip, composed of a small platinum coil, and after the solvent has been allowed to evaporate at room temperature, the probe is inserted into the source. The sample is then subject to fast temperature ramping. DCI does not seem to be the most suitable mass-spectrometric method for analysis of dissolved polymer/additive matrices, because ... 

Whereas the use of conventional fast atom bombardment (FAB) in the analysis of polymer/additive extracts has been reported (see Section 6.2.4), the need for a glycerol (or other polar) matrix might render FAB-MS analysis of a dissolved polymer/additive system rather unattractive (high chemical background, high level of matrix-, solvent- and polymer-related ions, complicated spectra). Yet, in selected cases the method has proved quite successful. Lay and Miller [53] have developed an alternative method to the use of sample extraction, cleanup, followed by GC in the quantitative analysis of PVC/DEHP with plasticiser levels as typically found in consumer products (ca. 30 %). The method relied on addition of the internal standard didecylphthalate (DDP) to a THF solution of the PVC sample with FAB-MS quantitation based on the relative signal levels of the [MH]+ ions of DEHP and DDP obtained from full-scan spectra, and on the use of a calibration curve (intensity ratio m/z 391/447 vs. mg DEHP/mg DDP). No FAB-matrix was added. No ions associated with the bulk of the PVC polymer were observed. It was... 

Gas chromatographic methods are used for the analysis of organic additives extracted from polymers with solvents and other liquid media or evolved by heating. 

As with sampling, laboratory extraction equipment must be clean. In addition, extraction equipment must be compatible with the analyte of interest. It also must not add any of the analyte or an interfering analyte to the sample during extraction. This is particularly important because of the low levels of analyte being determined and because most laboratories will not have new, disposable equipment. 

Just one extraction performed on a solution of a complicated sample will likely not result in total or at least sufficient separation of the analyte from other interfering solutes. Not only will these other species also be extracted to a certain degree with the analyte, but some of the analyte species will likely be left behind in the original solvent as well. Thus, the analyst will need to perform additional extractions on both the extracting solvent, to remove the other solutes that were extracted with the analyte, and the original solution, to remove additional analyte that was not extracted the first time. One can see that dozens of such extractions may be required to achieve the desired separation. Eventually, however, there would be a separation. The process is called countercurrent distribution. 

Humidity Chemical degradation, swelling, diffusion, additive extraction, cracking, hydrolysis... 

The removal of protein by filtration is a convenient way to avoid the interference of protein in the NMR measurement. However, this method requires that the analyte is not physically associated with the protein otherwise, ultrafiltration will remove the analyte along with the protein. In addition, extractables from the devices employed to remove the protein may be introduced into the sample. Therefore, proper controls must be prepared and analyzed. Despite these... 

Propylene carbonate is a good solvent of the rhodium precursor [Rh(acac) (00)2] and the phosphite ligand BIPHEPHOS and can thus be used as the catalyst phase in the investigation of the isomerizing hydroformylation of trans-4-octene to n-nonanal in a biphasic system [24]. As already mentioned, the reaction products can be extracted with the hydrocarbon dodecane. Instead of an additional extraction after the catalytic reaction, we carried out in-situ extraction experiments, where the products are separated from the catalytic propylene carbonate phase while the reaction is still in progress. Conversion of 96% and selectivity of 72% was achieved under comparably mild conditions (p(CO/H2) = 10 bar, T = 125 °C, 4 h, substrate/Rh = 200 1). 

The submitters obtained the yields indicated by washing the gummy precipitate with two 25-ml. portions of benzene the checkers observed that additional extraction at this point is required, and they recommend extraction with a total of four 25-ml. portions of warm benzene. 

This diversity in solvent properties results in large differences in the distribution ratios of extracted solutes. Some solvents, particularly those of class 3, readily react directly (due to their strong donor properties) with inorganic compounds and extract them without need for any additional extractant, while others (classes 4 and 5) do not dissolve salts without the aid of other extractants. These last are generally used as diluents for extractants, required for improving then-physical properties, such as density, viscosity, etc., or to bring solid extractants into solution in a liquid phase. The class 1 type of solvents are very soluble in water and are useless for extraction of metal species, although they may find use in separations in biochemical systems (see Chapter 9). 

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