Atom-transfer radical-polymerization

Atom transfer radical polymerization (ATRP) is an example of a reversible-deactivation radical polymerization. Like its counterpart, ATRA, or atom transfer radical addition, ATRP is a means of forming a carbon-carbon bond with a transition metal catalyst. The polymerization from this method is called atom transfer radical addition polymerization (ATRAP). As the name implies, the atom transfer step is crucial in the reaction responsible for uniform polymer chain growth. ATRP (or transition metal-mediated living radical polymerization) was independently discovered by Mitsuo Sawamoto and by Krzysztof Matyjaszewski in 1995.ATRP usually employs a transition metal complex as the catalyst with an alkyl halide as the initiator (R-X). Various transition metal complexes, namely those of Cu, Fe, Ru, Ni, and Os, have been employed as catalysts for ATRP. In an ATRP process, the dormant species is activated by the transition metal complex to generate radicals via one electron transfer process. Simultaneously the transition metal is oxidized to higher oxidation state. This reversible process rapidly establishes an equilibrium that is predominately shifted to the side with very low radical concentrations. The number of polymer chains is determined by thenumber of initiators. Each growing chain has the same probability to propagate with monomers to form living/dormant polymer chains (R-Pn-X). As a result, polymers with similar molecular weights and narrow molecular weight distribution can be prepared.There are five important variable components of atom transfer radical polymerizations. They are the monomer, initiator, catalyst, ligand, and solvent. The following section breaks down the contributions of each component to the overall polymerization.The radical concentration in normal ATRP can be calculated via the following equation:ATRP enables the polymerization of a wide variety of monomers with different chemical functionalities, proving to be more tolerant of these functionalities than ionic polymerizations. It provides increased control of molecular weight, molecular architecture and polymer composition while maintaining a low polydispersity (1.05-1.2). The halogen remaining at the end of the polymer chain after polymerization allows for facile post-polymerization chain-end modification into different reactive functional groups. The use of multi-functional initiators facilitates the synthesis of lower-arm star polymers and telechelic polymers. In a normal ATRP, the concentration of radicals is determined by the KATRP value, concentration of dormant species, and the / ratio. In principle, the total amount of Cu catalyst should not influence polymerization kinetics. However, the loss of chain end functionality slowly but irreversibly converts CuI to CuII. Thus initial / ratios are typically 0.1 to 1. When very low concentrations of catalysts are used, usually at the ppm level, activator regeneration processes are generally required to compensate the loss of CEF and regenerate a sufficient amount of CuI to continue the polymerization. Several activator regeneration ATRP methods were developed, namely ICAR ATRP, ARGET ATRP, SARA ATRP, eATRP, and photoinduced ATRP. The activator regeneration process is introduced to compensate the loss of chain end functionality, thus the cumulative amount of activator regeneration should roughly equal the total amount of the loss of chain end functionality.