Direct polymer reaction of poly(styrene-co-maleic anhydride): Polymeric imidization

Abstract

Using direct polymer reaction of poly(styrene-co-maleic anhydride) (SMA), a synthesis of copolymer of styrene and N-aryl succinimide (SMI) has been investigated. SMI copolymers were synthesized from SMA copolymers by a concerted two-step reaction, which consisted of the condensation reaction (step 1) of SMA with aromatic amine to prepare a precursor, succinamic acid, for imide formation and the cyclodehydration reaction (step 2) of succinamic acid. In this article, the application of Searle's preparation method of N-aryl or N-alkyl maleimide to the direct polymer reaction for SMI was attempted. Compared with synthesis of monomeric imides, the imide formation in polymeric condition appeared to be a little more sensitive to the reaction condition. The optimum condition for maximum conversion was examined in terms of time, temperature, and the amount of reactants.

Effect of poly(styrene‐co‐maleic anhydride) imidization on the miscibility and phase‐separation temperatures of poly(styrene‐co‐maleic anhydride)/poly(vinyl methyl ether) and poly(styrene‐co‐maleic anhydride)/ poly(methyl methacrylate) blends

“…To calculate the degree of conversion of the imidization reaction with eq. (1),13 the peak at 1602 cm −1 on the SMI spectrum was used because, as shown in Figure 1, this peak was not modified by the reaction: where parameters A 0 and A t are the ratios of the absorbance at 1780 cm −1 to that at 1602 cm −1 (taken from Fig. 1) before and after modification with aniline, respectively.…”

Erratum

“…It is well known that PSMA copolymers exhibit unique properties as wetting agents for the protection of surfaces and that they improve both water resistance and thermal resistance of composite materials 53, 59. To become water soluble, the copolymer needs to be hydrophilized by (partial) ring‐opening of the maleic anhydride units.…”

“…An advantage of this method is that while the RAFT endgroup is being removed from the polymer chains, and thus the color is removed, the maleic anhydride units of the PSMA copolymer are simultaneously ring‐opened, which renders them water soluble 66. In the experiments carried out in this study, a three‐fold molar excess of ammonia over the maleic anhydride units was used to ensure that all the maleic anhydride units would react with ammonia53 and a 20‐fold molar excess of ammonia to polymer was used to fully remove the thiocarbonyl thio moiety from the polymer chains.…”

“…The PSMA copolymers were intended for use as surfactant for the formation of nanocapsules in the aqueous phase and, therefore, the PSMA copolymers needed to be transformed into water soluble polymers. This was accomplished via reaction with a three‐fold molar excess of a 25% ammonia solution with respect to the maleic anhydride units 53. The water soluble polymer was then precipitated in THF before use to remove excess ammonia, because TetraThiol contains ester groups that can be cleaved via nucleophilic attack.…”

Fluorescent ROMP Monomers and Copolymers for Biomedical Applications

“…Grubbs' third generation catalyst was synthesized as reported previously . The exo ‐oxanorbornene‐imide precursors 4‐(2‐aminoethyl)‐3,6‐epoxy‐1,2,3,6‐tetrahydrophthalimide S1 and exo ‐4‐(2‐bromoethyl)‐3,6‐epoxy‐1,2,3,6‐tetrahydrophthalimide S2 were synthesized analogous to literature procedures, as described in the Supporting Information. The syntheses of monomers M4 and M5 and polymers P4 and P5 are given in the Supporting Information.…”