1070-4272/05/7812-2002 C 2005 Pleiades Publishing, Inc.
Russian Journal of Applied Chemistry, Vol. 78, No. 12, 2005, pp. 2002!2005. Translated from Zhurnal Prikladnoi Khimii, Vol. 78, No. 12, 2005,
Original Russian Text Copyright + 2005 by Galibeev, Mukhametzyanova, Kochnev, Arkhireev, Yakimov.
AND POLYMERIC MATERIALS
Anionic Copolymerization of C-Butyrolactone and 2,4-Toluene
Diisocyanate in the Presence of Triethylamine
S. S. Galibeev, E. A. Mukhametzyanova, A. M. Kochnev,
V. P. Arkhireev, and R. V. Yakimov
Kazan State Technological University, Kazan, Tatarstan, Russia
Received May 25, 2005
Abstract-Anionic copolymerization of 2,4-toluene diisocyanate with g-butyrolactone in the presence of
triethylamine was performed. The chemical structure of the copolymer obtained was determined by IR and
H NMR spectroscopy, and some kinetic features of the process were revealed.
Lactones are valuable monomers for preparing
polyesters with unique properties, showing promise
both as structural materials and as biologically active
substances in medicine .
The capability of various lactones to undergo poly-
merization strongly depends essentially on the ring
strain. In particular, b-propiolactone spontaneously
polymerizes under mild conditions ; e-caprolactone
undergoes ring opening under the action of organo-
metallic catalysts at 60380oC; g-butyrolactone (g-BL)
does not undergo homopolymerization even in the
presence of Ziegler3Natta catalysts but copolymerizes
with a wide variety of monomers (vinyl monomers,
cyclic acetals, amines, amides, ketenes, carboxy hy-
drides of amino acids) .
In this study, we examined the possibility of copoly-
merization of g-BL with 2,4-toluene diisocyanate (TDI)
in the presence of triethylamine (TEA). The choice
of TDI as comonomer was governed by the fact that,
in the presence of TEA, it can induce ring opening
of some heterocyclic compounds  that do not
undergo homopolymerization under these conditions.
The copolymers were prepared in a solvent (ace-
tone) at 20oC. The catalyst (TEA) concentration
was 0.02 mol %. The amount of the unchanged mono-
mer was determined by extraction with acetone in
a Soxhlet apparatus for 8 h.
The reaction of TDI with g-BL was studied by
NMR spectroscopy with a Tesla-100 spectrometer op-
erating at 100 MHz. Acetone-d
was used as solvent
and reference. The mid-IR spectra of the copoly-
mers were recorded on a Bruker FT-IR spectropho-
tometer. Samples were pelletized with KBr, using
a hydraulic press. The molecular mobility of the poly-
mers was studied by pulsed NMR spectroscopy on
a relaxometer operating at 20 MHz.
The thermal analysis was performed with a Q-1500
derivatograph (MOM, Hungary) at a heating rate of
3 deg min
To determine the physicomechanical characteris-
tics, we obtained films of TDI3g-BL copolymers from
acetone solutions by casting. The breaking stress s
was determined on an MR-500T-2 tensile-testing
machine at 20 + 2oC. The velocity of mobile clamps
was 100 mm min
The reaction rate constants were determined as
described in .
The IR spectra of TDI3g-BL copolymers contained
new bands absent in the spectra of the starting mono-
mers (Fig. 1): at 349033400 (N3H stretching vibra-
Fig. 1. IR spectrum of 2,4-TDI3g-BL copolymer. Reactant
molar ratio 1 : 1. (T) Transmission and (
n) wave number.