Reversible addition fragmentation chain transfer copolymerization: influence of the RAFT process on the copolymer composition

Feldermann, Achim; Toy, Andrew Ah; Phan, H.; Stenzel, Martina H.; Davis, Thomas P.; Barner‐Kowollik, Christopher

doi:10.1016/j.polymer.2004.04.016

Cited by 77 publications

(69 citation statements)

References 46 publications

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“…Hence, the cumulative and instantaneous mole fractions in the copolymer are about the same. This experimental fact (and subsequent analysis) is considered "best practice," and is used throughout the reactivity ratio estimation literature (see, for example, [10,[12][13][14]16,17]). …”

Section: Samplementioning

confidence: 99%

Computational Package for Copolymerization Reactivity Ratio Estimation: Improved Access to the Error-in-Variables-Model

Scott

Penlidis

2018

Processes

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Abstract:The error-in-variables-model (EVM) is the most statistically correct non-linear parameter estimation technique for reactivity ratio estimation. However, many polymer researchers are unaware of the advantages of EVM and therefore still choose to use rather erroneous or approximate methods. The procedure is straightforward but it is often avoided because it is seen as mathematically and computationally intensive. Therefore, the goal of this work is to make EVM more accessible to all researchers through a series of focused case studies. All analyses employ a MATLAB-based computational package for copolymerization reactivity ratio estimation. The basis of the package is previous work in our group over many years. This version is an improvement, as it ensures wider compatibility and enhanced flexibility with respect to copolymerization parameter estimation scenarios that can be considered.

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Section: Samplementioning

confidence: 99%

Computational Package for Copolymerization Reactivity Ratio Estimation: Improved Access to the Error-in-Variables-Model

Scott

Penlidis

2018

Processes

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“…Feldermann et al [138] have compared the conventional and the RAFT copolymerization for three comonomer systems, MMA-Sty, MA-Sty, and MMA-BA. In these cases, the differences between the Mayo plots, which report the copolymer composition vs. the proportion of comonomers in the initial polymerization medium, are rather weak.…”

Section: Copolymerizationmentioning

confidence: 99%

Experimental Requirements for an Efficient Control of Free‐Radical Polymerizations via the Reversible Addition‐Fragmentation Chain Transfer (RAFT) Process

Favier

Charreyre

2006

Macromol. Rapid Commun.

436

347

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Summary: Reversible addition‐fragmentation chain transfer (RAFT) polymerization is a recent and very versatile controlled radical polymerization technique that has enabled the synthesis of a wide range of macromolecules with well‐defined structures, compositions, and functionalities. The RAFT process is based on a reversible addition‐fragmentation reaction mediated by thiocarbonylthio compounds used as chain transfer agents (CTAs). A great variety of CTAs have been designed and synthesized so far with different kinds of substituents. In this review, all of the CTAs encountered in the literature from 1998 to date are reported and classified according to several criteria : i) the structure of their substituents, ii) the various monomers that they have been polymerized with, and iii) the type of polymerization that has been performed (solution, dispersed media, surface initiated, and copolymerization). Moreover, the influence of various parameters is discussed, especially the CTA structure relative to the monomer and the experimental conditions (temperature, pressure, initiation, CTA/initiator ratio, concentration), in order to optimise the kinetics and the efficiency of the molecular‐weight‐distribution control.

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“…The RAFT process is known to somewhat influence the (apparent) reactivity ratios of, for example, the copolymerization of methyl methacrylate and styrene though. 18 The reactivity of the monomers is not directly influenced, but differences in the rate of initiation of the monomers and during the pre-equilibrium phase can become apparent due to the typically smaller molecular weight in RAFT as compared to free-radical polymerizations, so that at very low conversion a higher reactivity can be found for one of the monomers. At the CTA concentration and conversion used for the determination of reactivity ratios in this study, such effects are likely negligible.…”

Section: Resultsmentioning

confidence: 99%

RAFT polymerization of alternating styrene‐pentafluorostyrene copolymers

Brummelhuis

Weck

2014

J. Polym. Sci. Part A: Polym. Chem.

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Reversible addition-fragmentation chain-transfer (RAFT) polymerization was used to control the alternating copolymerization of styrene and 2,3,4,5,6-pentaflurostyrene. The RAFT polymerization yields a high degree of control over the molecular weight of the polymers and does not significantly influence the reactivity ratios of the monomers. The controlled free-radical polymerization could be initiated using AIBN at elevated temperatures or using a redox couple (benzoyl peroxide/N,N-dimethylaniline) at room temperature, while maintaining control over molecular weight and dispersity. The influence of temperature and solvent on the molecular weight distribution and reactivity ratios were investigated. V C 2014

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Reversible addition fragmentation chain transfer copolymerization: influence of the RAFT process on the copolymer composition

Cited by 77 publications

References 46 publications

Computational Package for Copolymerization Reactivity Ratio Estimation: Improved Access to the Error-in-Variables-Model

Computational Package for Copolymerization Reactivity Ratio Estimation: Improved Access to the Error-in-Variables-Model

Experimental Requirements for an Efficient Control of Free‐Radical Polymerizations via the Reversible Addition‐Fragmentation Chain Transfer (RAFT) Process

RAFT polymerization of alternating styrene‐pentafluorostyrene copolymers

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