Unsaturated spectroscopy

An elegant example of a system investigated by UV-visible spectroscopy is the copolymer of styrene (molecule 1) and 1-chloro-l, 3-butadiene (molecule 2). These molecules quantitatively degrade with the loss of HCl upon heating in base solution. This restores 1,3-unsaturation to the butadiene repeat unit ... 

Measurement of Unsaturation. The presence of double bonds in a fatty acid side chain can be detected chemically or through use of instmmentation. Iodine value (IV) (74) is a measure of extent of the reaction of iodine with double bonds the higher the IV, the more unsaturated the oil. IV may also be calculated from fatty acid composition. The cis—trans configuration of double bonds may be deterrnined by infrared (59) or nmr spectroscopy. Naturally occurring oils have methylene-intermpted double bonds that do not absorb in the uv however, conjugated dienes maybe deterrnined in an appropriate solvent at 233 nm. 

Acetylene Derived from Hydrocarbons The analysis of purified hydrocarbon-derived acetylene is primarily concerned with the determination of other unsaturated hydrocarbons and iaert gases. Besides chemical analysis, physical analytical methods are employed such as gas chromatography, ir, uv, and mass spectroscopy. In iadustrial practice, gas chromatography is the most widely used tool for the analysis of acetylene. Satisfactory separation of acetylene from its impurities can be achieved usiag 50—80 mesh Porapak N programmed from 50—100°C at 4°C per minute. 

Amides can be titrated direcdy by perchloric acid ia a nonaqueous solvent (60,61) and by potentiometric titration (62), which gives the sum of amide and amine salts. Infrared spectroscopy has been used to characterize fatty acid amides (63). Mass spectroscopy has been able to iadicate the position of the unsaturation ia unsaturated fatty amides (64). Typical specifications of some primary fatty acid amides and properties of bisamides are shown ia Tables 5 and 6. 

Instmmental methods of analysis provide information about the specific composition and purity of the amines. QuaUtative information about the identity of the product (functional groups present) and quantitative analysis (amount of various components such as nitrile, amide, acid, and deterruination of unsaturation) can be obtained by infrared analysis. Gas chromatography (gc), with a Hquid phase of either Apiezon grease or Carbowax, and high performance Hquid chromatography (hplc), using siHca columns and solvent systems such as isooctane, methyl tert-huty ether, tetrahydrofuran, and methanol, are used for quantitative analysis of fatty amine mixtures. Nuclear magnetic resonance spectroscopy (nmr), both proton ( H) and carbon-13 ( C), which can be used for quaHtative and quantitative analysis, is an important method used to analyze fatty amines (8,81). 

Various methods can be used to analy2e succinic acid and succinic anhydride, depending on the characteristics of the material. Methods generally used to control specifications of pure products include acidimetric titration for total acidity or purity comparison with Pt—Co standard calibrated solutions for color oxidation with potassium permanganate for unsaturated compounds subtracting from the total acidity the anhydride content measured by titration with morpholine for content of free acid in the anhydride atomic absorption or plasma spectroscopy for metals titration with AgNO or BaCl2 for chlorides and sulfates, respectively and comparison of the color of the sulfide solution of the metals with that of a solution with a known Pb content for heavy metals. 

Most rubbers used in adhesives are not resistant to oxidation. Because the degree of unsaturation present in the polymer backbone of natural rubber, styrene-butadiene rubber, nitrile rubber and polychloroprene rubber, they can easily react with oxygen. Butyl rubber, however, possesses small degree of unsaturation and is quite resistant to oxidation. The effects of oxidation in rubber base adhesives after some years of service life can be assessed using FTIR spectroscopy. The ratio of the intensities of the absorption bands at 1740 cm" (carbonyl group) and at 2900 cm" (carbon-hydrogen bonds) significantly increases when the elastomer has been oxidized [50]. 

Unsaturated substituents of dioxolanes 36-38 and dioxanes 39-41 are prone to prototropic isomerization under the reaction conditions. According to IR spectroscopy, the isomer ratio in the reaction mixture depends on the temperature and duration of the experiment. However, in all cases, isomers with terminal acetylenic (36, 39) or allenic (37, 40) groups prevail. An attempt to displace the equilibrium toward the formation of disubstituted acetylene 41 by carrying out the reaction at a higher temperature (140°C) was unsuccessful From the reaction mixture, the diacetal of acetoacetaldehyde 42, formed via addition of propane-1,3-diol to unsaturated substituents of 1,3-dioxanes 39-41, was isolated (74ZOR953). 

The classic chemical technique for measuring the degree of unsaturation in diene polymers is iodometry (iodine value) [102]. Kubo et al. [103] extensively measured the iodine value to determine the amount of residual double bonds present in the HNBR. However, this method exhibited significantly poorer precision as compared with IR and NMR spectroscopies [99-101]. Acid... 

Hydrogenation of the a-unsaturated ester 32 was accompanied by extensive hydrogenolysis and NMR spectroscopy revealed that only 45% of a 3-deoxyhexose tetraacetate was present in the products and only one... 

Carboxylic acid groups can be detected by both and A3C NMR spectroscopy. Carboxyl carbon atoms absorb in the range 165 to 185 8 in the l3C NMR spectrum, with aromatic and unsaturated acids near the upheld end of the range (—165 8) and saturated aliphatic acids near the downfield end (—185 8). Nitrile carbons absorb in the range 115 to 130 8. 

In his pioneering work, Sus (1944) assumed that the final product of photodediazoniation of 2,1-diazonaphthoquinone (10.75) is indene-l-carboxylic acid (10.79, not the 3-isomer 10.78). He came to this conclusion on the basis of some analogies (in addition to an elemental analysis). Cope et al. (1956) as well as Yates and Robb (1957) found that the infrared spectrum of the product was consistent with an a,P-unsaturated acid. Later, Melera et al. (1974) verified the structure 10.78 by H NMR spectroscopy. Friedrich and Taggart (1975) showed that the equilibrium between 10.78 and 10.79 at 233 K lies on the side of the latter, but 10.78 clearly predominates at or above 0°C. Ponomareva et al. (1980) showed that not only 2,1-, but also 1,2-diazo-naphthoquinone yields indene-3- and not -1-carboxylic acid. 

A mixture of the a/J-unsaturated ester (14mmol), t-butyldimethylsilane (18 mmol) and tris(triphenylphosphine)rhodium(i) chloride (0.56 mmol) was placed in a pre-heated (100°C) oil bath, and the course of reaction monitored by i.r. spectroscopy. On completion (ca. 30 min) the product was isolated by direct distillation (60-88%). 

Ultraviolet spectroscopy metal in water complexes, 2, 309 redox potentials and, 1,498 Ultraviolet-visible spectroscopy, 1, 243 Umbellicomplexone metallofluorescent indicator, 1. 558 Undecametallic complexes, 1, 167 Uni thiol chelating agent heavy metal poisoning, 6. 767 Unsaturated compounds hydrogenation... 

Ultralow-monol polyols, 223 Ultrapek, 327, 328 Ultraviolet (UV) radiation, 209 Ultraviolet spectroscopy, 490 Unimolecular micelle, 58 United States, phenolic production in, 375 Unsaturated maleate/O-phthalate/ 1,2-propanediol polyester prepolymer, 101-102 Unsaturated polyester resins (UPRs), 19, 29-30, 58-59... 

As previously discussed, solvents that dissolve cellulose by derivatization may be employed for further functionahzation, e.g., esterification. Thus, cellulose has been dissolved in paraformaldehyde/DMSO and esterified, e.g., by acetic, butyric, and phthalic anhydride, as well as by unsaturated methacrylic and maleic anhydride, in the presence of pyridine, or an acetate catalyst. DS values from 0.2 to 2.0 were obtained, being higher, 2.5 for cellulose acetate. H and NMR spectroscopy have indicated that the hydroxyl group of the methy-lol chains are preferably esterified with the anhydrides. Treatment of celliflose with this solvent system, at 90 °C, with methylene diacetate or ethylene diacetate, in the presence of potassium acetate, led to cellulose acetate with a DS of 1.5. Interestingly, the reaction with acetyl chloride or activated acid is less convenient DMAc or DMF can be substituted for DMSO [215-219]. In another set of experiments, polymer with high o -celliflose content was esterified with trimethylacetic anhydride, 1,2,4-benzenetricarboylic anhydride, trimellitic anhydride, phthalic anhydride, and a pyridine catalyst. The esters were isolated after 8h of reaction at 80-100°C, or Ih at room temperature (trimellitic anhydride). These are versatile compounds with interesting elastomeric and thermoplastic properties, and can be cast as films and membranes [220]. 

The effect of antioxidants such as hindered phenohcs, secondary amine, and thioester on the radiation cross-linking efficiency of LDPE has been reported [260]. Amount of cross-linking at a given dose decreases with aU the antioxidants, the thioester being the most effective. IR absorption spectroscopy has been used to demonstrate dose-rate dependence of trani -vinylene unsaturation in irradiated Marlex 50 PE [261]. When the irradiated polymer is stored in vacuum a decrease is observed in trani-vinylene absorbance over a period of several weeks. After high dose-rate irradiation the decay is preceded by an initial increase. These phenomena have been ascribed to the reaction of trapped radicals. 

Complexes with unsaturated ligands (a-vinyl. a-allyl, and alkynyl) have been reported, each prepared from Fe(TPP)CI with the appropriate Grignard (vinyl, 2- methylvinyl.2,2-dimethylvinyl,allyl,or2-methylallyl)orlithiumreagent(LiC= C-n-Pr or LiC CPh) and observed by NMR spectroscopy (Scheme 4). The vinyl and alkynyl complexes are stable in solution at 25 C, whereas the allyl species decompose quickly if allowed to warm to room temperature. All were too reactive to be purihed by chromatography. The vinyl and allyl complexes show characteristic low spin behavior, although the temperature dependence of the vinyl... 

Unsaturated conjugated organic radicals are another group of unstable molecules studied by matrix IR spectroscopy, pyrolytic mass spectrometry... 

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