Abstract
The chain length distribution (CLD) of a reversible deactivation radical polymerization at full conversion is shown to be a negative binomial distribution with parameters that are simple functions of the number-average degree of polymerization and either the chain transfer constant (in the case of polymerizations that incorporate a reversible chain transfer step) or the concentrations of dormant polymer chains and deactivating agent and the rate constants of propagation and deactivation (other types of RDRP). Expressions for the CLD at intermediate conversions are also derived, and shown to be consistent with known expressions for the number-average degree of polymerization and dispersity. It is further demonstrated that these CLDs are well-approximated by negative binomial distributions with appropriate choice of parameters. The negative binomial distribution is thus a useful model for CLDs of reversible deactivation radical polymerizations.
Highlights
Reversible deactivation radical polymerization (RDRP) encompasses a range of polymerization techniques techniques developed developed over over the the last 25 years that permit the synthesis of well-defined, relatively narrowly-dispersed polymers via via a radical process.process
A similar approach to that of Tobita and Konkolewicz et al is used to show that the chain length distribution (CLD) of a polymer produced by an ideal RDRP batch process at full conversion is given by the negative binomial distribution with parameters CS and DPn /(DPn + CS ) (Equation (7))
We define an ideal RDRP as one in which all rate constants are independent of chain length and conversion, and no termination or other side reactions take place
Summary
Reversible deactivation radical polymerization (RDRP) encompasses a range of polymerization techniques techniques developed developed over over the the last 25 years that permit the synthesis of well-defined, relatively narrowly-dispersed polymers via via a radical process. The fundamental feature of RDRP is that dormant narrowly-dispersed polymers dormant polymer chains are reversibly activated to form propagating radicals which can grow by adding one or more monomer units before returning to to the the dormant dormant state state (Scheme (Scheme 1). Scheme mechanism of the deactivation step instep reversible deactivation radical
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