Analysis of Functional Homopolymers

The following section will describe the principal treatment of different types of molecular heterogeneity. Emphasis will be on the analysis of functional homopolymers (telechelics, macromonomers), copolymers (statistical, block, graft), and polymer blends. A detailed description of all experimental steps will be given for one or two representative examples of each group. Information on the application of the described procedures to different heteropolymer structures will be summarized briefly in the Sect. 5.1. 

Oligomers and polymers with reactive functional groups have been used extensively to prepare a great variety of polymeric materials. In many cases the behavior of these functional homopolymers is largely dependent on the nature and number of functional groups. In a number of important applications the functional groups are located at the end of the polymer chain macromolecules with terminal functional groups are usually termed telechelics or macromonomers . To characterize them it is necessary to have information not only about their molar mass but also on their functionality. 

When functional homopolymers are synthesized, in addition to macromolecules of required functionality, functionally defective molecules are formed (see Fig. 4). For example, if a target functionality of f = 2 is required, then in the normal case species with f = 1, f = 0 or higher functionalities are formed as well [7], Deviation of the average functionality from the pre-assigned one may result in a decreased or increased reactivity, cross-linking density, surface activity etc. Each functionality fraction has its own molar mass distribution. Therefore, to fully describe the chemical structure of a functional homopolymer, the determination of the molar mass distribution (MMD) and the functionality type distribution (FTD) is required. 

With respect to the chromatographic system, three different cases can be encountered (see Fig. 5) as follows. 

The functional groups do not manifest themselves chromatographically. The calibration curves for fractions of diflerent functionality coincide, and the molar 

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