Solvent extraction of additives

Classical Solvent Extractions of Additives from Polymers... 

Spell and Eddy [58] have described IR spectroscopic procedures for the determination of up to 500 ppm of various additives in PE pellets following solvent extraction of additives at room temperature. They showed that lonol (2,6-di- -butyl-p-cresol) and Santonox R... 

Tecator supplies units for carrying out organic solvent extractions on polymers. The Soxtec HT2-HT6 systems are recommended for carrying out solvent extractions of additives in polymers and rubbers. 

As an alternative to wet ehemical routes of analysis, this monograph deals mainly with the direct deformulation of solid polymer/additive compounds. In Chapter 1 in-polymer spectroscopic analysis of additives by means of UV/VIS, FTIR, near-IR, Raman, fluorescence spectroseopy, high-resolution solid-state NMR, ESR, Mossbauer and dielectrie resonance spectroscopy is considered with a wide coverage of experimental data. Chapter 2 deals mainly with thermal extraction (as opposed to solvent extraction) of additives and volatiles from polymerie material by means of (hyphenated) thermal analysis, pyrolysis and thermal desorption techniques. Use and applieations of various laser-based techniques (ablation, spectroscopy, desorption/ionisation and pyrolysis) to polymer/additive analysis are described in Chapter 3 and are critically evaluated. Chapter 4 gives particular emphasis to the determination of additives on polymeric surfaces. The classical methods of... 

Selective mass spectrometry. Rudewicz and Munson used selective mass spectrometry (SIMS) for the determination of additives in polypropylene without the need for prior solvent extraction of additives. 

Separation Processes. The product of ore digestion contains the rare earths in the same ratio as that in which they were originally present in the ore, with few exceptions, because of the similarity in chemical properties. The various processes for separating individual rare earth from naturally occurring rare-earth mixtures essentially utilize small differences in acidity resulting from the decrease in ionic radius from lanthanum to lutetium. The acidity differences influence the solubiUties of salts, the hydrolysis of cations, and the formation of complex species so as to allow separation by fractional crystallization, fractional precipitation, ion exchange, and solvent extraction. In addition, the existence of tetravalent and divalent species for cerium and europium, respectively, is useful because the chemical behavior of these ions is markedly different from that of the trivalent species. 

For solvent extraction of pentavalent vanadium as a decavanadate anion, the leach solution is acidified to ca pH 3 by addition of sulfuric acid. Vanadium is extracted in about four countercurrent mixer—settler stages by a 3—5 wt % solution of a tertiary alkyl amine in kerosene. The organic solvent is stripped by a soda-ash or ammonium hydroxide solution, and addition of ammoniacal salts to the rich vanadium strip Hquor yields ammonium metavanadate. A small part of the metavanadate is marketed in that form and some is decomposed at a carefully controlled low temperature to make air-dried or fine granular pentoxide, but most is converted to fused pentoxide by thermal decomposition at ca 450°C, melting at 900°C, then chilling and flaking. 

For solvent extraction of a tetravalent vanadium oxyvanadium cation, the leach solution is acidified to ca pH 1.6—2.0 by addition of sulfuric acid, and the redox potential is adjusted to —250 mV by heating and reaction with iron powder. Vanadium is extracted from the blue solution in ca six countercurrent mixer—settler stages by a kerosene solution of 5—6 wt % di-2-ethyIhexyl phosphoric acid (EHPA) and 3 wt % tributyl phosphate (TBP). The organic solvent is stripped by a 15 wt % sulfuric acid solution. The rich strip Hquor containing ca 50—65 g V20 /L is oxidized batchwise initially at pH 0.3 by addition of sodium chlorate then it is heated to 70°C and agitated during the addition of NH to raise the pH to 0.6. Vanadium pentoxide of 98—99% grade precipitates, is removed by filtration, and then is fused and flaked. 

An alternative mode for dehydrobenzoannulene decomposition was recently reported by Vollhardt et al. [58]. Non-planar hybrid 81, prepared in low yield via cyclodimerization of known triyne 82 [Eq.(3)], reacted explosively at ca. 250°C to give a nearly pure carbon residue. Solvent extraction of the black powder failed to yield soluble materials such as fullerenes however, analysis of the residue by TEM showed formation of bucky onions and bucky tubes [59], in addition... 

For polymer/additive analysis complete dissolution is not a prerequisite. Rather, the solvent should at least swell the polymer by diffusion, which allows the physically blended additives to dissolve. True dissolution occurs predominantly when polymer chain lengths are small, on the order of 5000-10 000 Da. Solvent choice for dissolution or extraction should take into account restrictions imposed by further analysis steps (compatibility with chromatographic and/or spectroscopic requirements). When microwave extraction of additives from a polymer is followed by HPLC analysis, the solvent must be compatible with the HPLC mobile phase so that solvent exchange is not required before analysis. 

More recently, some novel pressurised procedures for extraction of additives from polymers have been developed (Table 3.3). The principal objectives of all these techniques, such as SEE [89], MAE [90] and pressurised fluid extraction (PEE), is to replace the conventional extraction methods by shortening the extraction time, reduction in solvent use and automation. 

Reflux extraction of additives and wax from polyolefins was reported [116]. Subsequently, the additives were adsorbed onto an adsorbent (Florisil) and the wax was removed from the extract before chromatography. Boiling extractions of SBR are described in ASTM D 1416-89 1 g of rubber is extracted by boiling in two 100 mL portions of 75/25 vol% isopropyl alcohol/toluene. Reflux heating with strong solvents, such as THF, dichloromethane or chloroform has been reported [117]. Reflux extraction has also been used for the 3 h extraction of caprolactam and oligomers from PA6 in boiling methanol. 

Applications The broad industrial analytical applicability of microwave heating was mentioned before (see Section 3.4.4.2). The chemical industry requires extractions of additives (antioxidants, colorants, and slip agents) from plastic resins or vulcanised products. So far there have been relatively few publications on microwave-assisted solvent extraction from polymers (Table 3.5). As may be seen from Tables 3.27 and 3.28, most MAE work has concerned polyolefins. 

In order to perform extraction of additives or dissolution of polymers, solvents that absorb microwave energy are necessary. This is more important than direct absorption of microwave energy by the polymer or additives. When microwave extraction of additives... 

Successful extraction of additives from polymeric matrices requires a proper selection of organic solvents. Solvent choice was based on the following solvent properties ... 

Applications Open-column chromatography was used for polymer/additive analysis mainly in the 1950-1970 period (cf. Vimalasiri et al. [160]). Examples are the application of CC to styrene-butadiene copoly-mer/(additives, low-MW compounds) [530] and rubbers accelerators, antioxidants) [531]. Column chromatography of nine plasticisers in PVC with various elution solvents has been reported [44], as well as the separation of CHCI3 solvent extracts of PE/(BHT, Santonox R) on an alumina column [532]. Similarly, Santonox R and Ionol CP were easily separated using benzene and Topanol CA and dilaurylthiodipropionate using cyclohexane ethyl acetate (9 1 v/v) [533]. CC on neutral alumina has been used for the separation of antioxidants, accelerators and plasticisers in rubber extracts [534]. Column chromatography of polymer additives has been reviewed [160,375,376]. 

Recovery procedures have traditionally involved some form of solvent, gas or heat extraction from the bulk sample matrix. Some of these lend themselves to precolumn hyphenation (e.g. SFE, TD, Py, HS), as opposed to others (e.g. Soxhlet, ultrasonics). Extraction of additives should not be considered as an isolated step, because it may strongly influence the subsequent chromatographic separation. The success of an analysis may very often depend more on the extraction procedure than on the chromatographic separation. In hyphenation there should be compatibility between the sample preparation and subsequent chromatographic analysis. 

Solvents play an important role in polymer/additive analysis, namely for extraction of additives and dissolution of polymeric material, as a chromatographic liquid and as a window in spectroscopy. A solvent should generally have the following properties ... 

Solvent extraction and addition of a doping reagent (2% lithium chloride in methanol)... 

Solvent extraction of the total lipid extracts from ceramic sherds and charred surface residues Isolation of DAGs and TAGs on silica solid phase cartridges Formation of lithiated adducts from the TAG fraction by addition of 2% lithium chloride in methanol... 

The amount of the total petroleum hydrocarbons measured by this method depends on the ability of the solvent used to extract the hydrocarbon from the environmental media and the absorption of IR light by the hydrocarbons in the solvent extract. In addition, the method (EPA 418.1) is not specific to hydrocarbons and does not always indicate petroleum contamination (e.g., humic acid, a nonpetroleum hydrocarbon, may be detected by this method). 

In addition to linalyl acetate, the oil contains linalool and other terpene alcohols, as well as their acetates. When the volatile components are evaporated, a distinct ambergris note develops that is attributed to oxidative degradation products of sclareol [515-03-7] [746-750a]. Sclareol is the main component in the concrete, obtained by solvent extraction of S. sclarea L. leaves [750b]. 

While the method described here uses thermal desorption to release the volatiles from the trap directly to the GC, another method less often used is solvent extraction of the trap. Even though this will result in a lower sensitivity as the complete trap contents are diluted in solvent, an advantage is the possibility for multiple injections. Additionally, cold traps rather than adsorbent traps are also used to trap volatiles (Badings et al., 1985) although the water and C02 that are also condensed can pose GC difficulties. 

Many variants of the Purex (Plutonium Uranium Reduction Extraction) process23S based on TBP extraction have been developed but a basic outline flowsheet is illustrated in Figure 38. This shows the so-called early split flowsheet most commonly used in existing plants. It involves the separation of the uranium and plutonium using two different back-extractant streams during the first solvent extraction cycle. Additional solvent extraction cycles are then carried out independently on the uranium and plutonium streams to effect further purification. An alternative arrangement is the iate split flowsheet used at the Cap La Hague plant in France, and the... 

Coal rank has a considerable influence on the nature and amount of extracts obtained by the solvent extraction of coal (Kiebler, 1945). In addition, the soluble products of the extraction, whether they be called extracts or (incorrectly) bitumen, vary according to the means by which they are obtained. 

In addition to solvent extraction of lignans, a dry mechanical method for concentrating the lignan SDG was developed by Madhusudhan et al (2000). As a result, the content of SDG increased from 1290 and 1430 mg/100 g in whole Neche and Omega seed, respectively, to 2760 and 2380 mg/100 g in the hull-rich fractions (Madhusudhan et al, 2000). 

In addition to the above tests, which attempt to detect refining, there are other tests that indicate solvent extraction of the oil. As many oils are solvent extracted, and because solvent extraction usually produces an oil unsuitable for culinary use without refining, then tests for solvent extracted oil are also relevant. These are ... 

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