Vinyl polymers, microstructure analysis

The determination of the microstructure of vinyl polymers is not merely a characterisation tool. Each polymer molecule is unique, and each polymer chain is a record of the history of its formation, including mis-insertions, rearrangements, the incorporation of co-monomers, and the mode of its termination. NMR analysis of polymers can therefore be used to provide detailed mechanistic and kinetic information. This approach has been applied particularly successfully to the microstructure, i. e. the sequence distribution of monomer insertions, of polypropylene, giving rise to a wealth of studies far too numerous to cover here. Progress in this area has recently been summarised in two excellent and very comprehensive review articles [122, 123[. Here we will cover only the most fundamental aspects of stereoselective polymerisations. 

Pyrolysis GC has been used in the determination of compositional analysis and microstructure of chlorinated polyethylene (CPE). This method utilized specific aromatic compounds which were formed through dehydrochlorination of trimers after pyrolysis of CPE polymers at elevated temperatures. The composition and microstructure calculation was based on the difference between the levels of ethylene and vinyl chloride trimers formed [19-22]. 

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