1-Amino-4,5-8-naphthalenetricarboxylic acid-1,8-lactam-4,5-imide-containing macrocycles: Synthesis, molecular modeling and polymerization - Polyimides and Other High Temperature Polymers - page 183

1-Amino-4,5-8-naphthalenetricarboxylic
acid-1,8-lactam-4,5-imide-containing macrocycles:
Synthesis, molecular modeling and polymerization
PATRICIA PONCE, LIOUDMILA FOMINA, PATRICIA GARCÍA and
SERGUEI FOMINE ∗
Instituto de Investigaciones en Materiales, Universidad Nacional Autónoma de México,
Apartado Postal 70-360, CU, Coyoacán, México DF 04510, México
Abstract—Novel macrocycles containing 1-amino-4,5-8-naphthalenetricarboxylic acid-1,8-lactam-
4,5-imide and 1,4,5-8-naphthalenetetracarboxylic bisimide fragments have been synthesized by the
high temperature pseudo high dilution acylation of the corresponding diols with isopththaloyl chlo-
ride, 4,4'- and 2,2'-dichlorocarbonyl biphenyls with up to 60% yield. An important side reaction
that impedes cyclization was found to be the reaction of diol OH groups with HCl during the acyla-
tion. The ring strain in synthesized macrocycles and model cycles was estimated using the isodes-
mic reaction approach at B3LYP/6-311+G(d,p)//HF/3-21G level of theory. Lactamimide containing
macrocycles were found to be more strained as compared to those containing bisimide. The ring
opening polymerization (ROP) of synthesized macrocycles in the molten state shows that the driv-
ing force for this process is the strain release on ring opening. The ROP of lactamimide containing
macrocycles was found to be an efficient way to obtain lactamimide containing polymers, otherwise
difficult to synthesize.
Keywords : Macrocycles; ring opening polymerization; molecular modeling.
1. INTRODUCTION
The preparation of engineering thermoplastics via ROP is commercially attractive
for a number of reasons. The ROP reaction would convert a low molecular
weight, low viscosity cyclic precursor into a high molecular weight polymer
without formation of any by-product. In case of intractable polymers, ROP offers
a unique opportunity for the reactive processing of these polymers. The discovery
by Brunelle and coworkers of the high yield synthesis and facile polymerization
of cyclic polycarbonates [1] has sparked much interest in the macrocyclic mono-
mer technique. In the past 15 years this area has been rapidly extended to other
systems such as cyclic esters [2, 3], amides [4], aryl ethers [5-7], aramids [8] and