1070-4272/05/7804-0613 C 2005 Pleiades Publishing, Inc.
Russian Journal of Applied Chemistry, Vol. 78, No. 4, 2005, pp. 613!616. Translated from Zhurnal Prikladnoi Khimii, Vol. 78, No. 4, 2005,
Original Russian Text Copyright + 2005 by Nikolaeva, Osadchev.
AND POLYMERIC MATERIALS
Supramolecular Structure of the Polyamidine!Bisphenol System
M. N. Nikolaeva and A. Yu. Osadchev
Institute of Macromolecular Compounds, Russian Academy of Sciences, St. Petersburg, Russia
Received December 9, 2004
Abstract-Supramolecular organization of poly-1,10-decamethyleneacetamidine complexes with low-molec-
ular-weight bisphenols was studied by the
H nuclear magnetic relaxation and UV spectroscopy.
Noncovalent bonded networks are promising ma-
terials for development of new type polymer systems
exhibiting nonlinear optical properties . It is known
that hydrogen-bonded polymer networks formed in
the interaction of polymers of the polyamidine type
with dyes of the bisphenol type can also exhibit non-
linear optical properties . Therefore, a study of
the supramolecular structure of these polymer sys-
tems is of particular interest. It is known [3, 4] that
the hydrogen bond is formed between polyamidine
molecules and also between polyamidine and bis-
phenol (II) molecules both through the peripheral
hydroxo group of the dye and through the lateral hy-
droxo group of the quinoid form of the dye or keto
group of its main form  (structural formulas IIa
and IIb). However, the mobility and strength of inter-
chain interactions of the polyamidine are mainly
governed by the interactions of the peripheral hydroxy
groups of bisphenols.
We studied the interaction of poly-1,10-decameth-
yleneacetamidine (hereinafter, polyamidine)
with the following low-molecular-weight additives:
phenol (I), bis-(4-hydroxybenzylidene)acetone (II)
Synthesis and characteristics of poly-1,10-deca-
methyleneacetamidine were described in .
The degree of polymerization of the polyamidine
n = 50; glass transition point 4oC; melting point ap-
proximately 60oC . The melting points of phenol I,
bisphenol II, and bisphenol III are 43, 220, and
We used the NMR relaxation method, which allows
estimation of the mobility of polymer chains with
proton-containing groups. Introduction of new com-
pounds into the polymer composition alters the mo-
bility of macromolecules and, hence, the NMR relax-
ation time. The relaxation data offer information on
how the interaction of polymer chains changes .
Here, we studied the spin3spin relaxation time of poly-
amidine and its mixtures with low-molecular-weight
additives. Bisphenols dissolve in the polyamidine
melt. Poly-1,10-decamethyleneacetamidine and its
mixtures with bisphenols and phenol were heated to
180oC and allowed to stand at this temperature for
15 min; then the samples were cooled to the melting
point of polyamidine and the measurements began.
The mole fraction of the bisphenols in the mixture
with the polyamidine was varied from 0.05 to 0.35.
At these concentrations, the bisphenols are compatible
with the polymer.
The spin3spin relaxation times of protons T
polyamidine and a mixture of polyamidine with addi-
tion of low-molecular-weight bisphenols were meas-
ured in melts on an RRP-1 relaxometer in the temper-
ature range 703140oC. Each measurement was made