Macromolecular Associations in Solution

In dilute solution, all macromolecular chains undergo interactions with each other resulting in the so-called intermolecular excluded volume effect, corresponding to the intermolecular potential. This effect is also observed if one does not assume particular cohesive forces to occur between the macromolecular chains. Under these conditions, the second virial coefficient is calculated from the equation1,2)  

Since the compatibility of macromolecules is extensively discussed in many works on the -parameter18, it is treated here only briefly. When considering the compatibility of polymers, one must naturally give thought to weak inter-macromolecular interactions, for example, van der Waals force, dipole-dipole interaction, and so on. 

In these aggregation phenomena, the formation of intermacromolecular complexes is attributed to the fact that macromolecules with complementary binding sites interact with each other almost stoichiometrically in solution due to certain secondary binding forces. In this review, the formation of complementary complexes in synthetic macromolecular systems is mainly discussed. 

2 Secondary Binding Forces Between Intermacromolecular Complexes 

Intramolecular interactions were introduced for the first time by van der Waals in 1873 he thus attempted to explain the deviation of the real gas from the ideal gas. In order to apply the ideal gas law equation to the behavior of real gases, allowance should be made for the attractive and repulsive forces occurring between molecules. From that time on, the dipole moment theory of Debye (1912) and the dispersion energy or induced dipole theory by London (1930) were the main driving forces of the research about intermolecular interactions. 

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