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 184

imides [9]. The most recent coverage of ROP of cyclic esters can be found in
[10].

The present authors have recently reported the synthesis and characterization of
polylactamimides, a novel class of polymers combining good thermostability,
with luminescent and nonlinear optical properties [11-13]. However, in some
cases intractable products were obtained. The macrocyclic monomer technique
could be a new promising approach for the synthesis of polylactamimides via re-
active processing of macrocyclic monomers. Recent theoretical study of ROP of
lactamimide-containing macrocycles showed that this process was enthalpy
driven [14] unlike macrocylcic polycarbonates where the polymerization pro-
ceeded due to entropy gain on ring opening [15]. However, Kricheldorf et al. re-
cently discussed the formation of cyclic polyesters as a kinetically controlled
reaction [16]. Therefore, the successful ROP of lactamide containing macrocycles
is a challenging problem involving careful selection, design and synthesis of the
corresponding macrocyclic systems showing ring strain to undergo ROP.
This paper describes the molecular design and synthesis of lactamimide-
containing macrocycles, as well as their molecular modeling and polymerization.

2. EXPERIMENTAL PART

2.1. Materials
All reagents were used as received from Aldrich.
N,N'-Bis(6-hydroxyhexyl)-1,4,5-8-naphthalenetetracarboxylic bisimide ( 1 )

was prepared according to [11] with 91% yield, T m = 209°C.

N,N'-Bis(6-hydroxyhexyl)-1-amino-4,5-8-naphthalenetricarboxylic acid-1,8-

lactam-4,5-imide ( , DMSO

(45 ml), KOH (10.5 g (0.18 mol)) and methanol (60 ml) was stirred for 8 hrs un-
der oxygen flow at 70°C. The reaction mixture was acidified by dilute HCl, the
precipitate formed was filtered off and refluxed with a mixture of ethanol (100
ml) and conc. HCl (15 ml) for 2 hrs. The hot solution was filtered and poured into
water. The precipitate formed was filtered off and dried in vacuum: yield 97%,

2 ): A mixture of 3.018 g (0.0065 mol) of bisimide 1