**7. The use of highly ordered coordination compounds of copper for receiving the rigid polyurethane foam**

44 Polyurethane

[UPTI]: [Diamed-X] = 1:Y:

1. [CuCl2]:[АGМ]=1:4 (Y=0.9);

2. [CuCl2]:[DEHA]:[АGМ]=1:1,48:0,25 (Y = 0.9); 3. [CuCl2]:[ DEHA]:[АGМ]=1:1,48:0,25 (Y = 0.7); 4. [CuCl2]:[ DEHA]:[АGМ]=1:1,48:0,25 (Y = 0.5).

X) for urethane forming system based on UPTI.

Metal complex system, derived on the basis of CuCl2, DEHA and AGM was further used to modify polyurethanes. We measured the dependence of the volume resistivity (*ρv*) of

It turned out that the use of the worked out metal complex system caused the leap of *ρv* by 4 orders (10 000 times) observed at low concentrations of metal complex 0.01%. Here we should note that while using metal complex system based on CuCl2 and DEHA (no AGM) a stepwise drop of *ρv* was observed at much higher concentration of the complex - 0.1%.

**Figure 11.** Volume resistivity-concentration diagram of modified polyurethanes under molar ratio of

4

2

3

1

It was found that the use of metal complex systems based on CuCl2, DEHA and AGM could significantly reduce the dosage of curing agent 4,4-methylene-bis-o-chloroaniline (Diamed-

polyurethanes on the concentration of metal complex modifier (Fig. 11).

Metal complexes derived from CuCl2, DEHA and AGM were also tested as modifiers of the polyol component used in the manufacturing of rigid polyurethane foam. It was found that metal complex system based on CuCl2, DEHA and AGM had a significant impact on the rise and curing time of foam, reducing it (Fig. 12).

**Figure 12.** Rise (1) and curing (2) time of foam as a function of metal complex concentration based on [CuCl2]:[DEHA]:[АGМ]=1:1,48:0,25 in terms of CuCl2 (%)

It was also established that the increasing of the molar ratio of the AGM in metal complex system led to even greater decrease in rise and curing time of foam (Fig. 13).

In order to establish the role of the AGM in the foaming process it was loaded alone in polyol component (Figure 14). It was found that the AGM also reduces the rise and curing time of the foam. However, these parameters were more than two times higher than the parameters that caused the addition of metal complex system.

We also used metal complex system based on CuCl2 and DEHA as the control modifying system. In this case, in the wide range of concentrations of modifier the foam "collapsed". That is, the foam rose and the subsequently settled out. It should be also mentioned that the density of foam produced using metal complex system CuCl2 - DEHA - AGM did not change in comparison with polyurethane foam obtained by the unmodified polyol component.

Thus, these studies show a significant catalytic effect of the metal complex modifier on foaming. In this connection it should be noted that the polyol component is a complicated balanced system that contains catalysts of amine nature and organotin compounds already. Our results suggest that the metal complex systems act as a cocatalyst.

The Modification of Polyurethanes by Highly Ordered Coordination Compounds of Transition Metals 47

The next step was the research of such polyurethane foam key indicators as moisture absorption (Fig. 15) and water absorption (Fig. 16-17). It was found that the modified foam

**Figure 15.** Moisture absorption of rigid foam as a function of metal complex concentration based on

**Figure 16.** Water absorption of rigid foam as a function of metal complex concentration based on

[CuCl2]:[DEHA]:[АGМ]=1:1,48:0,25, where in terms of CuCl2 (%)

[CuCl2]:[DEHA]:[АGМ]=1:1,48:0,25 in terms of CuCl2 (%)

had enhanced characteristics as compared with unmodified polyurethane foam.

**Figure 13.** Rise (1) and curing (2) time of foam as a function of modifier concentration based on [CuCl2]:[DEHA]:[АGМ]=1:1,48:X, where Х is a mole fraction of AGM in the metal complex overall concentration (mol)

**Figure 14.** Rise (1) and curing (2) time of foam as a function of AGM concentration.

The next step was the research of such polyurethane foam key indicators as moisture absorption (Fig. 15) and water absorption (Fig. 16-17). It was found that the modified foam had enhanced characteristics as compared with unmodified polyurethane foam.

46 Polyurethane

concentration (mol)

**Figure 13.** Rise (1) and curing (2) time of foam as a function of modifier concentration based on [CuCl2]:[DEHA]:[АGМ]=1:1,48:X, where Х is a mole fraction of AGM in the metal complex overall

**Figure 14.** Rise (1) and curing (2) time of foam as a function of AGM concentration.

**Figure 15.** Moisture absorption of rigid foam as a function of metal complex concentration based on [CuCl2]:[DEHA]:[АGМ]=1:1,48:0,25 in terms of CuCl2 (%)

**Figure 16.** Water absorption of rigid foam as a function of metal complex concentration based on [CuCl2]:[DEHA]:[АGМ]=1:1,48:0,25, where in terms of CuCl2 (%)

The Modification of Polyurethanes by Highly Ordered Coordination Compounds of Transition Metals 49

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Davletbaeva I.M., Ismagilova A.I, Tyut'ko K.A., Burmakina G.V. & Kuzaev A.I. (1998) Reactions of isocyanates with the system based on CuCl2 - N,N'-Diethylhydroxylamine. *Russian Journal of General Chemistry*, Vol.68, No.6,

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**Author details** 

**9. References** 

1023)

929)

*269)*

pp.(348-369)

No.7, pp.(1889-1895)

pp.(1021-1027)

Vol.180, pp.(2073-2084)

*Advances in Polymer Science,* Vol.24, pp.(2-87)

polymers. *Macromolecules*, Vol.21, No.9, pp.(2887-2889)

pp.(87-90)

No.4, pp.(36-38)

*Chem. Soc.*, Vol.121, pp.(8825-8834)

Ruslan Davletbaev, Ilsiya Davletbaeva and Olesya Gumerova

*Kazan National Research Technological University, Russia* 

**Figure 17.** Water absorption of rigid foam as a function of modifier concentration based on [CuCl2]:[DEHA]:[АGМ]=1:1,48:X, where Х is a mole fraction of AGM in the metal complex overall concentration (mol)

In conclusion, it should be noted that in order to achieve a positive result very small amounts of modifiers are required.

#### **8. Conclusion**

We considered the methods of obtaining transition metal coordination compounds that were active in reactions with isocyanate and urethane groups.

The feature of these metal complexes is that the metal ions are arranged in a chain of atoms linked together by chloride bridges. It is established that the chain of exchange-coupled transition metal ions remains in the polyurethanes structured by metal complex compounds. This circumstance is the cause of stepwise decrease in the specific volume resistivity of the modified polyurethanes.

It seems to be interesting for further research in this field to study the effect of metal complex binding on the physical and mechanical properties of polyurethanes. The most promising materials in terms of improving strength properties and heat resistance are thermoplastic urethanes.

#### **Author details**

48 Polyurethane

concentration (mol)

**8. Conclusion** 

amounts of modifiers are required.

resistivity of the modified polyurethanes.

thermoplastic urethanes.

**Figure 17.** Water absorption of rigid foam as a function of modifier concentration based on [CuCl2]:[DEHA]:[АGМ]=1:1,48:X, where Х is a mole fraction of AGM in the metal complex overall

were active in reactions with isocyanate and urethane groups.

In conclusion, it should be noted that in order to achieve a positive result very small

We considered the methods of obtaining transition metal coordination compounds that

The feature of these metal complexes is that the metal ions are arranged in a chain of atoms linked together by chloride bridges. It is established that the chain of exchange-coupled transition metal ions remains in the polyurethanes structured by metal complex compounds. This circumstance is the cause of stepwise decrease in the specific volume

It seems to be interesting for further research in this field to study the effect of metal complex binding on the physical and mechanical properties of polyurethanes. The most promising materials in terms of improving strength properties and heat resistance are Ruslan Davletbaev, Ilsiya Davletbaeva and Olesya Gumerova *Kazan National Research Technological University, Russia* 

#### **9. References**


Davletbaeva I. M., Pyataev A. V., Kalachev K. E., Sadykov E. K. & Manapov R. A. (2006) Mössbauer study of structurally ordered iron coordination compounds and polyurethanes crosslinked by them. *Polymer Science,* Ser. A, 2006, Vol. 48, No. 6, pp.(612–617)

**Chapter 4** 

© 2012 Kozak and Lobko, 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 Kozak and Lobko, 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.

**Bottom-Up Nanostructured Segmented** 

**Polyurethanes with Immobilized** *in situ*

**and Properties Relationship** 

Additional information is available at the end of the chapter

due to complexing with polar groups of the polymer matrix.

**1.1. Materials, methods and instrumentations** 

Nataly Kozak and Eugenia Lobko

http://dx.doi.org/10.5772/48002

**1. Introduction** 

**Transition and Rare-Earth Metal Chelate** 

**Compounds – Polymer Topology – Structure** 

The formation of the polyurethanes (PU) with immobilized *in situ* co-ordinating metal compounds allows obtain structurally homogeneous systems with uniform dispersed nanosize metal containing sites. Aggregation of these metal chelate compounds is prevented

At the same time due to complex formation between the metal compound and polymer functional groups, the structuring of the forming matrix occurs on a nanoscale level. As a result, in the presence of small amounts of metal chelate compound (0,5-5%wt) both change of the polyurethane structure and properties can be observed. To understand the nature of above phenomena the influence of the weak interactions «macromolecule - metal» were

The present study investigates the formation of nanostructured linear and cross-linked polyurethanes (LPUs and CPUs, respectively) with immobilized *in situ* mono- and polyheteronuclear chelate compounds of rare-earth and transition metals. Influence of PU topology on self organization processes in polymer matrix and its properties is also subject of analysis.

Polypropylene glycol (PPG, MW 1000) was dried under vacuum at 120 oC for 2 h. Tolylene diisocyanate (mixture 80/20 of 2,4- and 2,6- isomers) (TDI) was distilled under vacuum.

analyzed on the metal-containing PUs structure, molecular dynamics and properties.

**Bottom-Up Nanostructured Segmented Polyurethanes with Immobilized** *in situ* **Transition and Rare-Earth Metal Chelate Compounds – Polymer Topology – Structure and Properties Relationship** 

Nataly Kozak and Eugenia Lobko

Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/48002
