Retardation in RAFT Polymerization: Does Cross-Termination Occur with Short Radicals Only?

Ting, S. R. Simon; Davis, Thomas P.; Zetterlund, Per B.

doi:10.1021/ma200831f

Cited by 50 publications

(48 citation statements)

References 49 publications

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“…The chain‐length‐dependence of fragmentation rate constant16 and of intermediate termination rate constant17, 18 has been proposed. In our experiments, BDB was used in the bulk polymerization, while polystyryl dithiobenzoate was used in the miniemulsion polymerization.…”

Section: Resultssupporting

confidence: 71%

Experimental Validation of Intermediate Termination in RAFT Polymerization with Dithiobenzoate via Comparison of Miniemulsion and Bulk Polymerization Rates

Suzuki

Nishimura

Kanematsu

et al. 2011

Macro Reaction Engineering

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To understand if either of two controversial models for the retardation by RAFT agents is applicable, styrene polymerization using dithiobenzoate as the RAFT agent is carried out in both bulk and miniemulsion systems with the same rates of radical generation and the same RAFT agent concentrations. Miniemulsion polymerization with average diameters of the miniemulsion droplets of ≈107 nm is by far faster than in bulk, and the obtained rate of polymerization agrees well with the calculated results assuming a bimolecular termination between propagating radical and intermediate radical, generated by the addition reaction of propagating radical to the RAFT agent, which shows that the intermediate termination is the major reason for rate retardation by the RAFT agent.magnified image

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Section: Resultssupporting

confidence: 71%

Experimental Validation of Intermediate Termination in RAFT Polymerization with Dithiobenzoate via Comparison of Miniemulsion and Bulk Polymerization Rates

Suzuki

Nishimura

Kanematsu

et al. 2011

Macro Reaction Engineering

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“…These involve the occurrence of (a) a missing step termination or (b) short chain termination. [128] Ting et al [129] have attempted to answer the question of whether crosstermination (between 4 and P n ) might involve short radicals only. They [129] compared the rates of polymerization when a macro-azo-initiator (5) and a polystyrene macro-RAFT agent (6) were used in a RAFT polymerization of styrene (St) (this system should involve no short chain radicals) to the situation where cumyl dithiobenzoate (11) was the RAFT agent and azoisobutyronitrile (AIBN) was used as initiator.…”

Section: Mechanisms For Retardationmentioning

confidence: 99%

Living Radical Polymerization by the RAFT Process – A Third Update

2012

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This paper provides a third update to the review of reversible deactivation radical polymerization (RDRP) achieved with thiocarbonylthio compounds (ZC(¼S)SR) by a mechanism of reversible addition-fragmentation chain transfer ( Chem. 2009Chem. , 62, 1402. This review cites over 700 publications that appeared during the period mid 2009 to early 2012 covering various aspects of RAFT polymerization which include reagent synthesis and properties, kinetics and mechanism of polymerization, novel polymer syntheses, and a diverse range of applications. This period has witnessed further significant developments, particularly in the areas of novel RAFT agents, techniques for end-group transformation, the production of micro/nanoparticles and modified surfaces, and biopolymer conjugates both for therapeutic and diagnostic applications.

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“…was observed at the beginning of polymerization that was followed by pseudo-first order kinetics. This kind of behavior had already been observed in the CDB-mediated polymerization of methacrylates [214] and its origin is the subject of a lively debate [215][216][217][218]. Fairly uniform polymers (Đ  1.20) with M n up to 14,000 Da were obtained that were chain extended with 2-(dimethylamino)ethyl methacrylate M44 (Entry 193, Table 3) to give double hydrophilic-hydrophilic AB diblock glycopolymers after deprotection of the sugar moieties (TFA/H 2 O 5:1 v/v, RT, 1 h).…”

Section: (Meth)acrylate Monomersmentioning

confidence: 67%

Synthesis of Glycopolymer Architectures by Reversible-Deactivation Radical Polymerization

Ghadban

Albertin

2013

Polymers

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This review summarizes the state of the art in the synthesis of well-defined glycopolymers by Reversible-Deactivation Radical Polymerization (RDRP) from its inception in 1998 until August 2012. Glycopolymers architectures have been successfully synthesized with four major RDRP techniques: Nitroxide-mediated radical polymerization (NMP), cyanoxyl-mediated radical polymerization (CMRP), atom transfer radical polymerization (ATRP) and reversible addition-fragmentation chain transfer (RAFT) polymerization. Over 140 publications were analyzed and their results summarized according to the technique used and the type of monomer(s) and carbohydrates involved. Particular emphasis was placed on the experimental conditions used, the structure obtained (comonomer distribution, topology), the degree of control achieved and the (potential) applications sought. A list of representative examples for each polymerization process can be found in tables placed at the beginning of each section covering a particular RDRP technique.

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Retardation in RAFT Polymerization: Does Cross-Termination Occur with Short Radicals Only?

Cited by 50 publications

References 49 publications

Experimental Validation of Intermediate Termination in RAFT Polymerization with Dithiobenzoate via Comparison of Miniemulsion and Bulk Polymerization Rates

Experimental Validation of Intermediate Termination in RAFT Polymerization with Dithiobenzoate via Comparison of Miniemulsion and Bulk Polymerization Rates

Living Radical Polymerization by the RAFT Process – A Third Update

Synthesis of Glycopolymer Architectures by Reversible-Deactivation Radical Polymerization

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