New step growth polymers via reissert compound chemistry

Abstract

Reissert compounds are the result of the formal addition of acyl cyanides across the CH=N bonds of aromatic heterocyclic compounds or acyclic imines. The chemistry of this class of compounds is primarily based upon the acidity of the CH(CN)‐NCOR moiety and the nucleophilic reactivity of the conjugate base. Three methodologies for application of this chemistry to the synthesis of polymers are summarized: 1) formation of polyamides by the “Reissert reaction” of suitable difunctional imines and diacid chlorides, 2) condensation of the anions of difunctional Reissert compounds with dielectrophiles such as dihaloalkanes and dialdehydes and 3) use of Reissert compound chemistry to construct novel monomers for use in traditional condensation polymerizations. All three methodologies are proven to be effective in the production of nitrogen containing polymers.

Heterocyclic monomers via reissert chemistry

“…In view of the impressive properties of poly(arylene ether)s on the one hand and N‐heterocyclic polymers on the other, the combination of these two classes of materials via Reissert compound chemistry was the objective of the work reported herein. This effort constituted a continuation of our applications of Reissert compounds in polymer chemistry12(e,f), 12(e), 17–19 in addition to our interest in the stereochemistry of these compounds 20…”

“…The polymerization of bis(Reissert compound) 25 17(a) with 1,10‐dibromodecane was performed by the NaH/DMF method (Scheme ). The rather rigid bis(Reissert compound) was not very soluble, requiring 15 mL of DMF per gram.…”

“…Polymerization of the more flexible and hence more soluble (CH 2 ) 10 bis(Reissert compound) 27 17(a) with 1,10‐dibromodecane and 1,5‐dibromopentane also led to polymers 28 with low intrinsic viscosities (Scheme , Table 1). The n = 10 polymer 28a did show promise with its intrinsic viscosity of 0.109 g/dL, but the low molecular weights of 28a and 28b were further evidenced by the brittle nature of their films cast onto Teflon from chloroform solution.…”

“…To a 50 mL two‐necked round bottom flask fitted with an N 2 inlet and outlet, 1.0000 g (1.606 mmol) of the bis(Reissert compound) 25 17(a) and 15 mL of dry DMF (distilled from CaH 2 and stored over molecular sieves) were added. The Reissert compound was insoluble but the mixture was stirred at 0 °C for 15 min, at which time NaH (0.135 g, 60% dispersion, 35 mmol) was added.…”

“…The C 10 bis(Reissert compound) 27 17(a) (0.8711 g, 1.000 mmol) was dissolved in 8 mL DMF at 0 °C under N 2 . Then, the dibromoalkane (1.000 mmol) was added and the mixture was stirred for 30 min, at which time NaH (0.096 g of 60% dispersion, 2.4 mmol) was added.…”