Polyolefins, extraction

Oligomeric hindered amine light stabilisers, such as Tinuvin 622 and Chimassorb 944, resist satisfactory analysis by conventional HPLC and have required direct UV spectroscopic analysis of a polyolefin extract [596], PyGC of an extract [618,648], or SEC of an extract [649]. Freitag et al. [616] determined Tinuvin 622 in LDPE, HDPE and PP by saponification of the polymer dissolution in hot toluene via addition of an... 

RPLC-FTTR of an Irganox 1010, Irganox PS800 containing polyolefin extract was reported with a thermospray /moving belt/DRIFT interface [483] detection limits of 100 ng were reported for this experimental device. LC-TSP-FTTR has also been used for the identification of other antioxidants, as shown in Figure 7.25 [500]. 

Rayon is unique among the mass produced man-made fibers because it is the only one to use a natural polymer (cellulose) directly. Polyesters, nylons, polyolefins, and acryflcs all come indirectly from vegetation they come from the polymerization of monomers obtained from reserves of fossil fuels, which in turn were formed by the incomplete biodegradation of vegetation that grew millions of years ago. The extraction of these nonrenewable reserves and the resulting return to the atmosphere of the carbon dioxide from which they were made is one of the most important environmental issues of current times. CeUulosic fibers therefore have much to recommend them provided that the processes used to make them have minimal environmental impact. 

Phase Separation. Microporous polymer systems consisting of essentially spherical, intercoimected voids, with a narrow range of pore and ceU-size distribution have been produced from a variety of thermoplastic resins by the phase-separation technique (127). If a polyolefin or polystyrene is insoluble in a solvent at low temperature but soluble at high temperatures, the solvent can be used to prepare a microporous polymer. When the solutions, containing 10—70% polymer, are cooled to ambient temperatures, the polymer separates as a second phase. The remaining nonsolvent can then be extracted from the solid material with common organic solvents. These microporous polymers may be useful in microfiltrations or as controlled-release carriers for a variety of chemicals. 

Other than fuel, the largest volume appHcation for hexane is in extraction of oil from seeds, eg, soybeans, cottonseed, safflower seed, peanuts, rapeseed, etc. Hexane has been found ideal for these appHcations because of its high solvency for oil, low boiling point, and low cost. Its narrow boiling range minimises losses, and its low benzene content minimises toxicity. These same properties also make hexane a desirable solvent and reaction medium in the manufacture of polyolefins, synthetic mbbers, and some pharmaceuticals. The solvent serves as catalyst carrier and, in some systems, assists in molecular weight regulation by precipitation of the polymer as it reaches a certain molecular size. However, most solution polymerization processes are fairly old it is likely that those processes will be replaced by more efficient nonsolvent processes in time. 

Analytical and test methods for the characterization of polyethylene and PP are also used for PB, PMP, and polymers of other higher a-olefins. The C-nmr method as well as k and Raman spectroscopic methods are all used to study the chemical stmcture and stereoregularity of polyolefin resins. In industry, polyolefin stereoregularity is usually estimated by the solvent—extraction method similar to that used for isotactic PP. Intrinsic viscosity measurements of dilute solutions in decahn and tetraHn at elevated temperatures can provide the basis for the molecular weight estimation of PB and PMP with the Mark-Houwiok equation, [rj] = KM. The constants K and d for several polyolefins are given in Table 8. 

Although the elastomer phase is essentially in particulate form, the tensile strength of the blend can be increased five-fold by increasing the cross-link density from zero to that conventionally used in vulcanisation processes, whilst tension set may be reduced by over two-thirds. Since the thermoplastic polyolefin phase may be completely extracted by boiling decalin or xylene, there is apparently no covalent chemical bonding of elastomer and thermoplastic phases. 

Wet processes involve mixing a hydrocarbon liquid or some other low-molecular -weight substance with a polyolefin resin, heating and melting the mixture, extruding the melt into a sheet, orientating the sheet either in the machine direction or biaxi-ally, and then extracting the liquid with a volatile solvent [6-8]. 

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. 

The polymer/additive system in combination with the proposed extraction technique determines the preferred solvent. In ASE the solvent must swell but not dissolve the polymer, whereas MAE requires a high dielectric solvent or solvent component. This makes solvent selection for MAE more problematical than for ASE . Therefore, MAE may be the preferred method for a plant laboratory analysing large numbers of similar samples (e.g. nonpolar or polar additives in polyolefins [210]). At variance to ASE , in MAE dissolution of the polymer will not block any transfer lines. Complete dissolution of the sample leads to rapid extractions, the polymer precipitating when the solvent cools. However, partial dissolution and softening of the polymer will result in agglomeration of particles and a reduction in extraction rate. 

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. 

Figure 3.14 Microwave extraction of 0.1 % Irganox 1010 from ground (20 mesh) polyolefins ( , PP O, LDPE +, HDPE) with 1,1,1-trichloroethane. After Freitag and John [96]. From W. Freitag and O. John, Angewandte Macromoleculare Chemie, 175, 181-185 (1990). Wiley-VCH, 1990. Reproduced by permission of Wiley-VCH...

The OSM MAP can be effectively applied to most of the organic additives for polyolefins. Its validity has been tested by comparing the OSM with traditional reflux extraction procedures for primary AOs (phenols), secondary AOs (aliphatic and aromatic phosphites ... 

UV3346) offer superior compatibility, low volatility, excellent resistance to extraction and contribute to heat stability. The nonextractable nature of these additives makes their quantification challenging. The quantification of Chimassorb 944 in polyolefins is possible using an UV absorption method after dissolution of the polymer [596]. 

High-MW hindered amine thermal stabiliser (HATS) formulations are designed for advanced extraction resistant long-term stabilisation, i.e. for use in extractive environments such as polyolefin pipes, fulfilling the stringent requirement of guaranteeing product lifetime of more than 50 years [565], These systems offer much better gas and hot water resistance than the low-MW phenolic antioxidant systems. Ethanox 330... 

Albemarle) has shown unique resistance to extraction from polyolefins. No radioactivity was detected in water run through a MDPE pipe stabilised with 14C-labelled Ethanox 330 for 10 months at ambient conditions, or in an accelerated 3-month test at 80 °C (limit of detection 25ppb). 

Applications Dissolution/reprecipitation is claimed to be the most widespread approach to polymer/additive analysis [603], but recent round-robins cast some doubt on this statement. Dissolution appears to be practised much less than LSEs. However, in cases where exhaustive extraction is difficult, e.g. for polyolefins containing high-MW (polymeric) additives, a dissolution/precipitation method is preferred. 

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],... 

GC is extensively used to determine phenolic and amine antioxidants, UV light absorbers, stabilisers and organic peroxide residues, in particular in polyolefins, polystyrene and rubbers (cf. Table 61 of Crompton [158]). Ostromow [159] has described the quantitative determination of stabilisers and AOs in acetone or methanol extracts of rubbers and elastomers by means of GC. The method is restricted to analytes which volatilise between 160 °C and 300 °C without decomposition. A selection of 47 reports on GC analysis of AOs in elastomers (period 1959-1982) has been published... 

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