From telomerization to living radical polymerization

Abstract

After a brief description of the various methods of telomer synthesis, the different types of transfer agents and monomers are given, showing the extremely wide variety of macromolecules that may be obtained through this route. Knowing the kinetics laws allows one to control the functionality and chain lengths, and so it is possible to control the oligomer architecture, essentially monofunctional and telechelic. Finally, the contribution of the techniques of telomerization to actual research on living radical polymerization is detailed. The great majority of the methods using the chain transfer reaction are a continuation of telomerization reactions [iodine transfer polymerization, atom transfer radical polymerization, reversible addition fragmentation chain transfer (RAFT), and macromolecule design through interchange of xanthes (MADIX)]. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3235–3243, 2000

Synthesis of block copolymers via atom transfer radical polymerization and ‘click chemistry’ grafted from pre-functionalized polypropylene surfaces using gamma irradiation

“…S2 †), consistent with a telopolymerization process. 23,31 As expected the transferdominated polymerizations yielded polymers with a PDI around 2.0. 1 H NMR and ESI-MS analyses confirmed the synthesis of confirms the structure predicted by NMR analysis.…”

Synthesis of block copolymers via atom transfer radical polymerization and ‘click chemistry’ grafted from pre-functionalized polypropylene surfaces using gamma irradiation

“…S2 †), consistent with a telopolymerization process. 23,31 As expected the transferdominated polymerizations yielded polymers with a PDI around 2.0. 1 H NMR and ESI-MS analyses confirmed the synthesis of confirms the structure predicted by NMR analysis.…”

Investigation of the Telomerization Kinetics of N-Isopropylacrylamide Using 3-Mercaptopropionic Hydrazide as Chain Transfer Agent

“…Besides their capacity to react as chain transfer agents, these molecules also supply a well-defined end group to the final polymer (telomer). Vinyl monomers that are suitable for conventional radical chain polymerization, such as ethylene, styrenes, acrylamides, or (meth)acrylates, can be used in telomerization. − …”

Incubation period in the 2,2,4,4‐tetramethyl‐1‐piperidinyloxy‐mediated thermal autopolymerization of styrene: Kinetics and simulations

“…Figure 6 shows the sensitivity of the model predictions to the value of k h for TEMPO from dimer 1. Very low values of this constant, such as 0.01 L mol À1 s À1 (gross estimation by Boutevin and Bertin 26 for this parameter at 120 8C), do considerably enlarge the induction period over the estimation of eq 3 and are therefore not likely. Toward a value of k h ¼ 0.5 L mol À1 s À1 , the length of the induction period reaches asymptotically the value predicted by eq 3.…”

Synthesis of block copolymers via atom transfer radical polymerization and ‘click chemistry’ grafted from pre-functionalized polypropylene surfaces using gamma irradiation

“…S2 †), consistent with a telopolymerization process. 23,31 As expected the transferdominated polymerizations yielded polymers with a PDI around 2.0. 1 H NMR and ESI-MS analyses confirmed the synthesis of confirms the structure predicted by NMR analysis.…”

Investigation of the Telomerization Kinetics of N-Isopropylacrylamide Using 3-Mercaptopropionic Hydrazide as Chain Transfer Agent

“…Besides their capacity to react as chain transfer agents, these molecules also supply a well-defined end group to the final polymer (telomer). Vinyl monomers that are suitable for conventional radical chain polymerization, such as ethylene, styrenes, acrylamides, or (meth)acrylates, can be used in telomerization. − …”

Incubation period in the 2,2,4,4‐tetramethyl‐1‐piperidinyloxy‐mediated thermal autopolymerization of styrene: Kinetics and simulations

“…Figure 6 shows the sensitivity of the model predictions to the value of k h for TEMPO from dimer 1. Very low values of this constant, such as 0.01 L mol À1 s À1 (gross estimation by Boutevin and Bertin 26 for this parameter at 120 8C), do considerably enlarge the induction period over the estimation of eq 3 and are therefore not likely. Toward a value of k h ¼ 0.5 L mol À1 s À1 , the length of the induction period reaches asymptotically the value predicted by eq 3.…”

Synthesis of block copolymers via atom transfer radical polymerization and ‘click chemistry’ grafted from pre-functionalized polypropylene surfaces using gamma irradiation

“…S2 †), consistent with a telopolymerization process. 23,31 As expected the transferdominated polymerizations yielded polymers with a PDI around 2.0. 1 H NMR and ESI-MS analyses confirmed the synthesis of confirms the structure predicted by NMR analysis.…”

Investigation of the Telomerization Kinetics of N-Isopropylacrylamide Using 3-Mercaptopropionic Hydrazide as Chain Transfer Agent

“…Besides their capacity to react as chain transfer agents, these molecules also supply a well-defined end group to the final polymer (telomer). Vinyl monomers that are suitable for conventional radical chain polymerization, such as ethylene, styrenes, acrylamides, or (meth)acrylates, can be used in telomerization. − …”

Incubation period in the 2,2,4,4‐tetramethyl‐1‐piperidinyloxy‐mediated thermal autopolymerization of styrene: Kinetics and simulations

“…Figure 6 shows the sensitivity of the model predictions to the value of k h for TEMPO from dimer 1. Very low values of this constant, such as 0.01 L mol À1 s À1 (gross estimation by Boutevin and Bertin 26 for this parameter at 120 8C), do considerably enlarge the induction period over the estimation of eq 3 and are therefore not likely. Toward a value of k h ¼ 0.5 L mol À1 s À1 , the length of the induction period reaches asymptotically the value predicted by eq 3.…”