**1. Introduction**

32 Polyurethane

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One of the ways to influence the chemical structure of polyurethanes is to use metal complex systems based on transition metal chlorides for their synthesis. The significance of this trend is conditioned by the ability of metal complexes to order the macromolecular chains, as well as affect the electrical properties of polyurethanes (Davletbaeva et al., 1996, 2001).

The synthesis of metal coordination polymers is a way of affecting the processes of crosslinking of macrochains; interchain and intraionic interactions; and, thereby, preparing polymer materials with special properties (Dirk et al., 1986; Kingsborough & Swager, 1999; Reynolds et al., 1985; Thuchide & Nishide, 1977; Wang & Reynolds, 1988). From the standpoint of designing materials with electric and magnetic properties, it is promising to form in a polymer matrix chains of transition metal ions bound by exchange interaction.

Conventional methods for the creation of interactions of this type in a polymer are primarily based on the presence of certain units in a macromolecule, e.g., those including the phthalocyanine and azomethine moieties. For example, metal atoms in metal phthalocyanine liquid crystalline complexes are bound to one another by chloride bridges and play the role of a spacer between phthalocyanine units, thus promoting overlap of electronic orbitals of parallel molecules (Shirai et al., 1977, 1979).

As a result, the electric conductivity of metal-coordination polymers obtained on the basis of these complexes is increased by a few orders of magnitude relative to undoped systems. The coordination bonding of comb-like liquid crystalline polymers can also give rise to stacked structures. Interaction between metal ions is revealed in such polymers, which is realized owing to the association of metal ions in an indirect manner, through ester oxygen bridges.

© 2012 Davletbaev et al., licensee InTech. This is an open access chapter distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. © 2012 Davletbaev et al., licensee InTech. This is a paper distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

However, this approach is seriously limited and cannot be used for the creation of stacked metal-coordinated fragments in a disordered polymer matrix (Brostow, 1990; Carrher, 1981; Serrano & Oriol, 1995).

The Modification of Polyurethanes by Highly Ordered Coordination Compounds of Transition Metals 35

N OH O

NH2 H C3

OCN


2

where Ar - NCO

Cu Cl Cl

Cu

Cl Cl

Cu

H C3

OCN

N H

+**.** +**.**


OCN

NH2

.

<sup>N</sup> CH3 <sup>H</sup>

NCO


Ar N N Ar

Ar N N Ar

CH3

O C

O C

O C

CH3 CH3

CH3 CH3

CH3 CH3

O C

O C

CH3 CH3

> CH3 CH3

Cl Cl

CH3 CH3

Cu Cl Cl

Cl Cl

Cu

Ar N N Ar

NCO H C3

H C3

<sup>N</sup> CH3 <sup>H</sup>

NCO

NCO

N CH3

<sup>H</sup> H3C

OCN

H3C NH


<sup>N</sup> + 2 Cu + 4 H + 4 Cl <sup>+</sup> <sup>+</sup> -

<sup>2</sup> <sup>+</sup>

+ H2O

2 CuCl2

N

OCN

Cu

Cl Cl Cu

Ar Ar N N O C

**Figure 1.** Formation of polynuclear complexes of azoaromatic compounds.

Cl Cl Cu

C O

C O

H3C H3C

H3C H3C

H C3

OCN

H C3

OCN

H3C

2 NCO

OCN

OCN

Metal complex structuring is promising in terms of the influence on properties of polyurethanes. The significance of this trend is conditioned by the ability of metal complexes to order the macromolecular chains, as well as affect the electrical properties of polyurethanes.
