Infrared polymer extracts

Fourier transfer near infrared Raman spectroscopy (400-10,000 cm ) is useful for the examination of additives in polymer extracts [31]. 

Cyasorb UV 531 ultraviolet absorber (2-hydroxy-4-n octoxybenzophenone) is determined in polyethylene by infrared spectroscopy of a polymer extract in amounts down to 0.02%. 

Synthetic solutions of DLTDP were prepared in the four aqueous and the alcoholic extractants. The DLTDP was added to 700 ml of each of the extractants at the 16 and the 75 ppm level as a solution of 5 ml of methyl alcohol. These solutions were then heated for 10 days at 60 °C in order to simulate the conditions occurring in an actual polymer extraction test. At the end of this period, DLTDP was extracted from the extractants with diethyl ether prior to analysis by the infrared procedure. 

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. 

Further, we examined the Heck reaction between w-butyl acrylate and 4-bromobenzotrifluoride 5 in the presence of 2 mol% Pd clusters in a singlevessel monomode m/w oven fitted with an infrared thermometer. 100% conversion with quantitative yield to the cinnamate was obtained after 5 min irradiation at 75 W/240 °C. We then repeated the reaction under conventional heating at 240 °C. After 3.5 min a black tarry gel formed. Extraction followed by GC analysis showed only cinnamate, but the tarry material (probably acrylate polymers/oligomers) could not be analysed. These experiments show that when clusters are present different results are obtained depending whether m/w heating or conventional heating is used. In principle, this could be the result of hot spots created on the metal clusters. 

Figure 5 Infrared spectrum of block copolymer residue after Soxhlet extraction of PVA core polymer with acetonitrile.

Always based on the use of IR spectrophotometry, a novel attenuated total reflection-Fourier-transform infrared (ATR-FTIR) sensor [42] was proposed for the on-line monitoring of a dechlorination process. Organohalogenated compounds such as trichloroethylene (TCE), tetrachloroethylene (PCE) and carbon tetrachloride (CT) were detected with a limit of a few milligrams per litre, after extraction on the ATR internal-reflection element coated with a hydro-phobic polymer. As for all IR techniques, partial least squares (PLS) calibration models are needed. As previously, this system is promising for bioprocess control and optimization. 

Bisphthalonitrile monomers were cured neat, with nucleophilic and redox co-reactants, or in combination with a reactive diluent. Dynamic mechanical measurements on the resulting polymers from -150 to +300°C turn up several differences attributable to differences in network structure. Rheovibron results were supplemented with solvent extraction, differential scanning calorimetry (DSC), vapor pressure osmometry, and infrared spectroscopy to characterize the state of cure. 

In this presentation, we report the characterization of HTE liquid polymers free from the interference of cyclic oligomers. Cyclic oli omers of the higher molecular weight HTE liquid polymers (Mn>1200), including commercial Hydrin 10 liquid polymers, were removed by extraction. The functionality of the liquid polymer was then determined, and structures are proposed as determined by infrared, carbon-13 and proton NMR, and field desorption mass spectroscopic analyses. 

Phenolic compounds have also been oxidatively polymerized to humic substances by clay minerals (29) and by the mineral fraction of a latasol (66). After a 10-day equilibration period, montmoril-lonite and illite clay minerals yielded 44 to 47% of the total added phenolic acids as humic substances whereas quartz gave only 9%. Samples of a latasol yielded over 63% of the total amount, from mixtures in varied proportion, of mono-, di- and trihydroxy phenolic compounds as humic substances (66). Extractions of the reaction products yielded humic, fulvic, and humin fractions that resembled soil natural fractions in color, in acid-base solubility, and in infrared absorption spectra. Wang and co-workers (67) further showed that the catalytic polymerization of catechol to humic substances was, enhanced by the presence of A1 oxide and increased with pH in the 5.0 to 7.0 range. Thus the normally very reactive products of Itgnin degradation can be linked into very stable humic acid polymers which will maintain a pool of potentially reactive phytotoxins in the soil. 

Figure 2.17. Infrared spectra of the synthesized FA (MW > 1000 Da) in the Mn(IV) oxide-pyrogallol system and the FA extracted from a Borosaprist (Terric Humisol). Reprinted from Wang, M. C., and Huang, P. M. (2000). Characteristics of pyrogallol-derived polymers formed by catalysis of oxides. Soil Sci. 165, 737-747, with permission from Lippincott Williams Wilkins.

Quantitative determinations of the thicknesses of a multiple - layered sample (for example, two polymer layers in intimate contact) by ATR spectroscopy has been shown to be possible. The attenuation effect on the evanescent wave by the layer in contact with the IRE surface must be taken into account (112). Extension of this idea of a step-type concentration profile for an adsorbed surfactant layer on an IRE surface was made (113). and equations relating the Gibbs surface excess to the absorbance in the infrared spectrum of a sufficiently thin adsorbed surfactant layer were developed. The addition of a thin layer of a viscous hydrocarbon liquid to the IRE surface was investigated as a model of a liquid-liquid interface (114) for studies of metal extraction ( Ni+2, Cu+2) by a hydrophobic chelating agent. The extraction of the metals from an aqueous buffer into the hydrocarbon layer was monitored kinetically by the appearance of bands unique to the complex formed. 

In this case study, which is extracted from reference 184, infrared dichroism is described as a means of separating the component dynamics in multicomponent polymer melts. What is necessary is the existence of distinct absorption peaks for at least one of the components. In the present problem, however, where two chains of identical chemistry but different molecular weights are mixed, there will not be any intrinsic differences in their absorption spectra. In this case it is necessary to label one of chains with a tag that will allow its presence in the blend to be revealed. For this purpose, deuteration of one of the chains is often used. This provides the labeled chain with an absorption of infrared light at the symmetric stretching vibration of the C-D bond, which occurs in the vicinity of 2180 cm-1. Fortunately, the unlabeled polymer contains no absorption peak at this location. It is important, however, to determine that the presence of a label on one species will not alter the physical response of the sample at a level that will affect the phenomena under study. For example, the labeling should not induce phase separation or cause unwanted specific interactions. 

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