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Optically active alternating copolymers of maleic acid and alkylvinylethers

✍ Scribed by Claude Villiers; Christian Braud; Michel Vert; Emo Chiellini; Massimo Marchetti


Publisher
Elsevier Science
Year
1978
Tongue
English
Weight
556 KB
Volume
14
Category
Article
ISSN
0014-3057

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✦ Synopsis


Alternating copolymers of maleic acid (MAc) with optically active alkylvinylethers (RVE)[R = (S)-l-methylpropyl, (R)-l-methylbutyl, (S)-2-methylbutyl, (S)-3-methylpentyl, (S)-4-methylhexyl, (S)-l-methylheptyl and (S)-3,7-dimethyloctyl] were obtained by hydrolysis in aqueous alkaline medium of the corresponding copolymers with maleic anhydride (MAn). i.r. Absorption spectra, viscosity and potentiometric titration curves are described as well as u.v., ORD and CD spectra recorded in ethanol and water. Conductometric titrations in non-aqueous medium confirm the alternance of dicarboxylic and ethereal structural units. It is shown that the nature of alkyl substituents strongly affects the ionization process of the first, carboxylic group. The u.v. bands connected with the n--~ n* electronic transitions of carboxylic chromophores are optically active and the ellipticities of the dichroic bands around 215 nm depend on the position of the asymmetric carbon atoms present in the side chain. Moreover for copolymers with ethereal structural unit containing an asymmetric carbon atom c~ with respect to the oxygen atom, the rotatory strength of such bands is dependent on the length of the alkyl substituents for measurements carried out in water, whilst no significant dependence is evident in measurements performed in ethanol. No ordered secondary structure is considered to account for these features which are probably due to asymmetric induction phenomena involving optically active side chains.


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Copolymers and terpolymers of maleic anhydride as insoluble supports for Co(H), Cu(II) and Mn(II) catalysts, have been synthesized. The structure of polymeric matrices were studied by 13C DD/CP/MAS NMR spectroscopy. Thermal properties of polymeric complexes were examined by DSC techniques. The compl