Itaconic acid applications

Fumaric and itaconic acids are also used as the diacid component. Most reaction formulations involve a mixture of a saturated diacid (iso- and terephthalic, adipic) with the unsaturated diacid or anhydride in appropriate proportions to control the density of crosslinking (which depends on the carbon-carbon double-bond content of the prepolymer) for specific applications [Parker and Peffer, 1977 Selley, 1988], Propylene glycol, 1,4-butanediol, neopentyl glycol, diethylene glycol, and bisphenol A are also used in place of ethylene glycol as the diol component. Aromatic reactants are used in the formulation to improve the hardness, rigidity, and heat resistance of the crosslinked product. Halogenated reactants are used to impart flame resistance. 

During the past decade, the properties and applications of the monoesters and diesters derived from itaconic acid have received growing interest because the monomers can be obtained biotechnologically and a great variety of related polymers can be synthesized thanks to two lateral esterifiable groups contained in the monomer [65]. The first work on poly(monomethyl itaconate) (PMMI)/ PVPo complexes was done by Bimendina et al. [66], and it was followed by Pe-... 

The asymmetric hydrogenation of itaconic acid (Scheme 21) and its derivatives132 has become adopted as something of a standard by which catalysts are compared. A selection of results is given in Table 2 (e.e.s only)133,76. Further applications of related reductions include the synthesis of the Renin inhibitor subunit 12 by reduction of 13 in 95% e.e.132 and the protease inhibitor 14 by reduction of 15 in this case in up to 84% e.e.134. For these processes the ligands of choice were either BINAP (in conjunction with Ru) or a derivative of BPPM (P7). 

Rh complexes of ferrocene-based ligands are very effective for the hydrogenation of several types of dehydroamino (2,3,29,41,42,44) and itaconic acid derivatives (4,5,28) as well as for enamide 45, enol acetate 26, and a tetrasubstituted C = C-COOH 21. Of particular interest are substrates that have unusual substituents (41,42,44) at the C = C moiety or are more sterically hindered than the usual model compounds (21,42). Table 15.10 lists typical examples with very high ee s and often respectable TONs and TOFs. Several industrial applications have already been reported using Rh-Josiphos and Ru-Josiphos (see Figure 15.7) as well as Rh-Walphos (Scheme 15.8). 

Itaconic acid was isolated in 1836 from the pyrolysis products of citric acid (7) and the pol3mierization of the ethyl ester was observed by SwAETS in 1873 (2). While many patents relating to the acid and its esters as monomers have issued since that time, only recently have reports begun to appear in the scientific journals. The voluminous patent literature describes the use of polymeric itaconic acid derivatives in such applications as protective and decorative coatings, synthetic fibers, oil additives and rigid plastics as well as many others. Several summaries of the patent art and present commercial applications are available (3). Such information has been omitted from this review, which is directed primarily toward chemical behavior of the itaconic monomers and polymers. 

Luskin LS (1974) Acidic monomers. 111. Itaconic acid. In Yocum RH, Nyquist EB (eds) Functional monomers, their preparation, polymerization and application, vol 1. Marcel Dekker, New York, p 465... 

ESR spectra of short-lived radicals in the liquid state. Applying it to the radical polymerization of AA, MAA, and itaconic acid (ITA), Fischer et al. <> -56) observed ESR spectra of monomer, dimer, and polymer radicals and discussed the conformations of these radicals in terms of the hyperfine splitting constants for their P-methylene protons. Ranby et al. 6i> extended its application to the radical polymerization of several monomers such as vinyl esters and butadiene and also to the copolymerization of binary monomer systems. However, the use of the thermal-redox radical-generating method has been chiefly restricted to reactions in aqueous solution. 

Water Soluble Poly(acrylic acid-co-itaconic acid-co-iV-vinylpyrrolidone) Materials Optimization of Monomer Ratios for Copolymer Application in Glass-Ionomer Type Dental Restoratives... 

The polymerization of itaconic acid seems not to have been studied very extensively, although industrial applications in copolymer systems appear to be of considerable interest. In view of the work of A. Katchalsky and coworkers [38] on the effect of pH on the polymerization of acrylic acid and methacrylic acid, analogous research on pH effects on itaconic acid reactions has been carried out to a limited extent [95, 96]. Typically, with a persulfate initiator in an aqueous solution at 50°C, the monomer is converted to an extent of 85-90% to its homopolymer within 35-45 hr. In the pH range of 2.3-3.8, the rate of polymerization is constant. As the pH increases, the rate becomes progressively slower and stops completely at a pH of 9. Generally, the last 5-10% of the monomer seems to be difficult to convert to polymer. 

Most textile acrylics contain 10-15% comonomers. For carbon fiber precursors lower comonomer levels are used (about 5%) comonomers are selected that promote the reactions in the aftertreatment (methyl acrylate, itaconic acid). Wet spinning is preferred because the cross-section can be controlled better then. In dry spinning skin formation can hardly be prevented and eventually the cross-section collapses into a "dog bone shape, which is not desirable in carbon fiber applications. Precursor filaments are drawn to much higher draw ratios (> lOx) than tex-... 

Poly(isopropyl vinyl ether-alt-MA), 316, 621 Poly(isopropyl-o-vinyl formal-alt-MA), 328 Poly(itaconic anhydride), 240 Poly(lauryl methacrylate-co-MA), 284 Poly(maleic acid) applications, 239, 261 ionization properties, 260 physical properties, 259 polyelectrolyte behavior, 260 solution properties, 259 synthesis by pyridine polymer, 259 thermal properties, 260 titration behavior, 260 Poly (maleic anhydride), 232, 239-262 analysis methods, 241, 245, 248, 249, 254,... 

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