Structural analysis of alkene/maleic anhydride copolymers

Abstract

Structural investigations on maleic anhydride (MAn) copolymers with ethene, propene and styrene, their products of hydrolysis, and their methyl half-esters by means of I3C NMR spectroscopy are presented. The spectra of 2,3-diethylsuccinic acid and its anhydrides in the erythro-and threo-configuration and of butylsuccinic acid and its anhydride were obtained and compared with the spectra of the copolymers. In each case the results show the formation of both threo(trans)-and erythro(c~)-structures. At a polymerization temperature of 60 "C the proportions were 88% threo to 12% erythro for ethene/MAn copolymers and 80% threo to 20% erythro for propene/MAn copolymers, a ratio which was confirmed also by the hydrolyzed forms. Copolymerization at 150°C leads, in the case of propene/MAn, to 67% threo and 33% erythro. The production of ethene/MA copolymer via the copolymerization of ethene and fumaric acid half-ester and its saponification to ethene/fumaric acid leads to a ratio of 38% threo to 62% erythro. These results are in accordance with the thermal stabilities of the configurations. In the case of styrene/MAn copolymer it is not possible to obtain a unique interpretation of the configurations from the spectra. For the conversion of propene/MAn and styrene/MAn copolymers by means of methanol to half-esters it can be derived from the I3C NMR spectra how many of the half-ester moieties are obtained in the neighbourhood of the methyl and phenyl groups, respectively, of the olefin. a) Revised manuscript of August 16, 1985.

Functional Films of Maleic Anhydride Copolymers under Physiological Conditions

“…t c nicely shows trend with smaller times for the smaller comonomers, as it can be expected according to the literature for the reactivity of the different copolymers discussed 22. Interestingly, in this context the difference for PEMA and PPMA due to the additional CH 3 group in the comonomer is very pronounced in contrast to steady state swelling characteristics at pH 7.4 where it followed the same scaling law with the same pre‐factor, as discussed above.…”

Isomerisation of Erythro‐ and Threo‐Succinyl Units in Alternating Alkene‐Maleic Acid Copolymers: A Promising Route to New Microstructures

“…The radical polymerisation of MAn with olefins results in limited erythro-contents of about 12-17% for ethene [7][8][9] and 20-33% for propene [8] as comonomer. No erythrounits were found for the isobutene copolymer.…”

“…[10,11] These contents can be varied using mono-or dialkylesters of maleic or fumaric acid as comonomers. [8,10] The non-cyclic monomers result in an increased content of erythrosuccinyl units. Using a mixture of such esters and MAn would allow the variation of the erythro-content but results in structural inhomogeneity because of the different reactivities of non-cyclic esters and MAn.…”

Polymerization of ?-caprolactone with maleic anhydride: Synthesis and characterization

“…Copolymerization of ethene,12, 13 propene,13 dienes,14 and styrene15–17 with maleic anhydride has been studied extensively. The cationic ring‐opening polymerization of 4‐methylene‐1,3‐dioxolane has also been studied 18, 19.…”