**Author details**

74 Polyurethane

System D·10-6, cm2/с

The solution of Со(асаса)3 5%wt.

**7. Conclusion** 

heterogeneity" of the systems.

where DF – one-particle ("Frenkel ") diffusion coefficient ; DL – collective ("Lagrangian") diffusion coefficient.

the spatial hindrances for the liquid molecule dynamics.

dielectric, surface etc. properties of the modified polyurethane.

segregation of metal containing centres at this boundary.

DF ·10-6, cm2/с

Probe liquid 3,52 3,18 0,35 8,0

in the probe liquid 3,33 3,04 0,29 8,7

CPU-0 (CH2Cl2) 2,71 2,40 0,31 11,5

CPU-Со5% (CH2Cl2) 1,85 1,32 0,53 28,6

CPU-Со5% (DMF) 1,25 0,89 0,36 28,8

The sharp decreasing of both the general and one-particle component of diffusion coefficient for the metal containing PU as compared with the metal-free PU indicates the appearance of

Immobilization *in situ* mono- and polyheteronuclear chelate compounds of transition and rare-earth metal in linear and cross-linked polyurethanes results in nanoscale structuring of forming polymer and is accompanied with polymer matrix enrichment by the nanosize heteroligand macro complexes of metal formed simultaneously with organic nanosize structures characteristic for metal-free polymer. Nanostructuring of formed in this way polyurethane favours creation of a new hierarchy in structural organization of the polymer as compared with metal free system as well as changes in dynamic, relaxation, optical,

Analysis of structural heterogeneity of metal-modified polymer indicates existence of two types of nanosize heterogeneities in the bulk of polyurethane. One of them is inherent to segmented PU and another is generated in the presence of transition metal chelate compound. The structural heterogeneity of PU influences the local segmental mobility of macro chains, resulting in "dynamic heterogeneity" as well as in "thermodynamic

The possible origin of the formation of the ordered micro regions is segmental structure of PU containing the soft and hard blocks with different complex ability relative to metal chelate compound. The PU's surface structure depends on the boundary "polymer-support" or "polymer-air". Concentration of PU less polar groups that form the weak complexes with metal chelate compound at the "polymer-support" boundary can facilitate the partial

**Table 9.** The diffusion parameters of the probe molecules in the swelled PU films

DL·10-6 , cm2/с

DL/D, %

> Nataly Kozak and Eugenia Lobko *Institute of Macromolecular Chemistry National Academy of Sciences of Ukraine, Ukraine*
