End groups are an important aspect of polymer synthesis and characterization. In polymer chemistry, they are functional groups that are at the very ends of a macromolecule or oligomer (IUPAC). In polymer synthesis, like condensation polymerization and free-radical types of polymerization, end-groups are commonly used and can be analyzed by nuclear magnetic resonance (NMR) to determine the average length of the polymer. Other methods for characterization of polymers where end-groups are used are mass spectrometry and vibrational spectrometry, like infrared and raman spectroscopy. These groups are important for the analysis of polymers and for grafting to and from a polymer chain to create a new copolymer. One example of an end group is in the polymer poly(ethylene glycol) diacrylate where the end-groups are circled.
thumbnail|right|End group example of poly(ethylene glycol) diacrylate with the end groups circled
End groups in polymer synthesis
End groups are seen on all polymers and the functionality of those end groups can be important in determining the application of polymers. Each type of polymerization (free radical, condensation or etc.) has end groups that are typical for the polymerization, and knowledge of these can help to identify the type of polymerization method used to form the polymer.
Step-growth polymerization
Step-growth polymerization involves two monomers with bi- or multifunctionality to form polymer chains. Many polymers are synthesized via step-growth polymerization and include polyesters, polyamides, and polyurethanes. A sub-class of step-growth polymerization is condensation polymerization.
Condensation polymerization
Condensation polymerization is an important class of step-growth polymerization, which is formed simply by the reaction of two monomers and results in the release of a water molecule. Since these polymers are typically made up of two or more monomers, the resulting end groups are from the monomer functionality. Examples of condensation polymers can be seen with polyamides, polyacetals and polyesters. An example of polyester is polyethylene terephthalate (PET), which is made from the monomers terephthalic acid and ethylene glycol. If one of the components in the polymerization is in excess, then that polymers functionality will be at the ends of the polymers (a carboxylic acid or alcohol group respectively).
900px|center|PET condensation polymerization from terephthalic and ethylene glycol, showing what occurs when each monomer is in excess
Free radical polymerization
The end groups that are found on polymers formed through free radical polymerization are a result from the initiators and termination method used. The "grafting from" approach involves, for example, generation of radicals along a polymer chain, which can then be reacted with monomers to grow a new polymer from the backbone of another. In "grafting from," the initiation sites on the backbone of the first polymer can be part of the backbone structure originally or generated in situ. Each technique has its advantages and disadvantages, which are details below.
NMR spectroscopy
The advantage of NMR for end groups is that it allows for not only the identification of the end group units, but also allows for the quantification of the number-average length of the polymer. End-group analysis with NMR requires that the polymer be soluble in organic or aqueous solvents. Additionally, the signal on the end-group must be visible as a distinct spectral frequency, i.e. it must not overlap with other signals. As molecular weight increases, the width of the spectral peaks also increase. As a result of this, methods which rely on resolution of the end-group signal are mostly used for polymers of low molecular weight (roughly less than 20,000 g/mol number-average molecular weight). By using the information obtained from the integration of a <sup>1</sup>H NMR spectrum, the degree of polymerization (X<sub>n</sub>) can be calculated. With knowledge of the identity of the end groups/repeat unit and the number of protons contained on each, the X<sub>n</sub> can then be calculated. For this example above, once the 1H NMR has been integrated and the values have been normalized to 1, the degree of polymerization is calculated by simply dividing the normalized value for the repeat unit by the number of protons continued in the repeat unit. For this case, X<sub>n</sub> = n = 100/2, and therefore X<sub>n</sub> = 50, or there are 50 repeat units in this monomer.
framed|center|Example of utility of NMR for end group analysis
Mass spectrometry
Mass spectrometry (MS) is helpful for the determination of the molecular weight of the polymer, structure of the polymer, etc. Although chemists utilize many kinds of MS, the two that are used most typically are matrix-assisted laser desorption ionization/time of flight (MALDI-TOF) and electrospray ionization-mass spectroscopy (ESI-MS). One of the biggest disadvantages of this technique is that much like NMR spectroscopy the polymers have to be soluble in some organic solvent. An advantage of using MALDI is that it provides the simpler data to interpret for end group identification compared with ESI, but a disadvantage is that the ionization can be rather hard and as a result some end groups do not remain intact for analysis.
center|400px|RAFT polymerization
The method for removal of thiocarbonyl containing end groups includes reacting the polymers containing the end-groups with en excess of radicals which add to the reactive C=S bond of the end group forming an intermediate radical (shown below). The remaining radical on the polymer chain can be hydrogenated by what is referred to as a trapping group and terminate; this results in a polymer that is free of the end groups at the α and ω positions.
center|900px|RAFT polymerization mechanism
Another method of end group removal for the thiocarbonyl containing end-groups of RAFT polymers is the addition of heat to the polymer; this is referred to as thermolysis. One method of monitoring thermolysis of RAFT polymers is by thermogravimetric analysis resulting in a weight-loss of the end group. An advantage of this technique is that no additional chemicals are required to remove the end group; however, it is required that the polymer be thermally stable to high temperature and therefore may not be effective for some polymers. Depending on the polymers sensitivity to ultraviolet radiation (UV) it has been reported in recent years that decomposition of end-groups can be effective, but preliminary data suggest that decomposition by UV leads to a change in the distribution of molecular weights of the polymer.
Surface modification using RAFT
Surface modification has gained a lot of interest in recent years for a variety of applications. An example of the application of free radical polymerizations to forming new architectures is through RAFT polymerizations which result in dithioester end groups. These dithioesters can be reduced to the thiol which can be immobilized on a metal surface; this is important for applications in electronics, sensing and catalysis. The schematic below demonstrates the immobilization of copolymers onto a gold surface as reported for poly(sodium 4-styrenesulfonate) by the McCormick group at the University of Southern Mississippi.