Infrared spectroscopy, oxidation methods

The carbonyl index is not a standard technique, but is a widely used convenient measurement for comparing the relative extent and rate of oxidation in series of related polymer samples. The carbonyl index is determined using mid-infrared spectroscopy. The method is based on determining the absorbance ratio of a carbonyl (vC = 0) band generated as a consequence of oxidation normalised normally to the intensity of an absorption band in the polymer spectrum that is invariant with respect to polymer oxidation. (In an analogous manner, a hydroxyl index may be determined from a determination of the absorbance intensity of a vOH band normalised against an absorbance band that is invariant to the extent of oxidation.) In the text following, two examples of multi-technique studies of polymer oxidation will be discussed briefly each includes a measure of a carbonyl index. 

A rapid Fourier transform infrared spectroscopy (FTIR) method based on the stoichiometric reaction of triphenylphosphine (TPP) with hydroperoxides has been developed and successfully applied to determination of PV of edible oils (32). The hydroperoxides present in oil samples react stoichiometrically with TPP to produce triphenylphosphine oxide (TPPO), which has an intense absorption... 

Transmission Fourier Transform Infrared Spectroscopy. The most straightforward method for the acquisition of in spectra of surface layers is standard transmission spectroscopy (35,36). This approach can only be used for samples which are partially in transparent or which can be diluted with an in transparent medium such as KBr and pressed into a transmissive pellet. The extent to which the in spectral region (typically ca 600 4000 cm ) is available for study depends on the in absorption characteristics of the soHd support material. Transmission ftir spectroscopy is most often used to study surface species on metal oxides. These soHds leave reasonably large spectral windows within which the spectral behavior of the surface species can be viewed. 

The performance of the V-Mg oxide catalyst was found to depend on its composition and the method of preparation. As to the composition, it was found that catalysts containing very small or very large amounts of vanadium were not selective. The better catalysts in terms of both activity and selectivity consisted of from about 10 to 60 wt% V2O5 (35). Analyses of these catalysts by X-ray diffraction, Auger electron spectroscopy, and infrared spectroscopy showed that they contained only two identifiable phases Mg orthovanadate (Mg3(V04)2) and MgO. Since MgO had low activity and poor selectivity under the reaction conditions employed, it was concluded that the active phase was Mg orthovanadate (Mg3(V04)2). Indeed, it was later shown that this compound was a selective catalyst (26). 

Other important tests are for acid and alkalinity number and for water content (266), because water content and alkalinity of the polyether glycol can influence the reaction with isocyanates. The standard ASTM test for acid and alkalinity number, ASTM D4662 (267), is not sensitive enough for the low acidity and alkalinity numbers of PTMEG, and special methods have been developed. A useful alkalinity number (AN) has been defined as milliequivalents KOH per 30 kg of PTMEG, as titrated in methanol solution with 0.005 N HC1 (268). Other useful nonstandard tests are for heavy metals, sulfated ash, and peroxide. The peroxides formed initially in oxidations are quickly transformed into carbonyl groups, which are detectable by infrared spectroscopy. On oxidation, a small C—O peak develops at 1726 cm-1 and can be detected in thick (0.5-mm) films. A relative ratio of this peak against an internal standard peak at 2075 C—O is sometimes defined as the carbonyl ratio. 

Reed 332) has reported that reaction of ethylene oxide with the a,(a-dilithiumpoly-butadiene in predominantly hydrocarbon media (some residual ether from the dilithium initiator preparation was present) produced telechelic polybutadienes with hydroxyl functionalities (determined by infrared spectroscopy) of 2.0 + 0.1 in most cases. A recent report by Morton, et al.146) confirms the efficiency of the ethylene oxide termination reaction for a,ta-dilithiumpolyisoprene functionalities of 1.99, 1.92 and 2.0j were reported (determined by titration using Method B of ASTM method E222-66). It should be noted, however, that term of a, co-dilithium-polymers with ethylene oxide resulted in gel formation which required 1-4 days for completion. In general, epoxides are not polymerized by lithium bases 333,334), presumably because of the unreactivity of the strongly associated lithium alkoxides641 which are formed. With counter ions such as sodium or potassium, reaction of the polymeric anions with ethylene oxide will effect polymerization to form block copolymers (Eq. (80) 334 336>). 

IR spectroscopy can be used to characterise not only different rubbers, but also to understand the structural changes due to the chemical modification of the rubbers. The chemical methods normally used to modify rubbers include hydrogenation, halogenation, hydrosilylation, phosphonylation and sulfonation. The effects of oxidation, weathering and radiation on the polymer structure can be studied with the help of infrared spectroscopy. Formation of ionic polymers and ionomeric polyblends behaving as thermoplastic elastomers can be followed by this method. Infrared spectroscopy in conjunction with other techniques is an important tool to characterise polymeric materials. 

Regarding ozonation processes, the treatment with ozone leads to halogen-free oxygenated compounds (except when bromide is present), mostly aldehydes, carboxylic acids, ketoacids, ketones, etc. [189]. The evolution of analytical techniques and their combined use have allowed some researchers to identify new ozone by-products. This is the case of the work of Richardson et al. [189,190] who combined mass spectrometry and infrared spectroscopy together with derivatization methods. These authors found numerous aldehydes, ketones, dicarbonyl compounds, carboxylic acids, aldo and keto acids, and nitriles from the ozonation of Mississippi River water with 2.7-3 mg L 1 of TOC and pH about 7.5. They also identified by-products from ozonated-chlorinated (with chlorine and chloramine) water. In these cases, they found haloalkanes, haloalkenes, halo aldehydes, haloketones, haloacids, brominated compounds due to the presence of bromide ion, etc. They observed a lower formation of halocompounds formed after ozone-chlorine or chloramine oxidations than after single chlorination or chlorami-nation, showing the beneficial effect of preozonation. 

The problem with sulfide catalysts (hydrotreatment) is to determine the active centres, which represent only part of their total surface area. Chemisorption of O2, CO and NO is used, and some attempts concern NIL, pyridine and thiophene. Static volumetric methods or dynamic methods (pulse or frontal mode) may be used, but the techniques do not seem yet reliable, due to the possible modification (oxidation) of the surface or subsurface regions by O2 or NO probe molecules or the kinetics of adsorption. CO might be more promising. Infrared spectroscopy, especially FTIR seems necessary to characterise co-ordinativcly unsaturated sites, which are essential for catalytic activity. CO and NO can also be used to identify the chemical nature of sites (sulfided, partially reduced or reduced sites). For such... 

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