scholarly journals Reversing RAFT Polymerization: Near-Quantitative Monomer Generation via a Catalyst-Free Depolymerization Approach

2021 ◽  
Author(s):  
Hyun Suk Wang ◽  
Nghia P. Truong ◽  
Athina Anastasaki
Keyword(s):  
Chain Transfer ◽  
Raft Polymerization ◽  
Controlled Radical Polymerization ◽  
Catalyst Free ◽  
Reversible Addition ◽  
Fundamental Research ◽  
New Applications ◽  
Raft Polymers ◽  
Glycol Methyl Ether ◽  
End Group

The ability to reverse controlled radical polymerization and regenerate the monomer would be highly beneficial for both fundamental research and applications, yet has remained very challenging to achieve. Herein, we report a near-quantitative (up to 92%) and catalyst-free depolymerization of various linear, bulky, crosslinked, and functional polymethacrylates made by reversible addition-fragmentation chain-transfer (RAFT) polymerization. Key to our approach is to exploit the high end-group fidelity of RAFT polymers to generate chain-end radicals via thermal homolytic cleavage of carbon-sulfur bond of the RAFT end-group at 120 °C. These radicals trigger a rapid unzipping of both conventional (e.g. poly(methyl methacrylate)) and bulky polymers (e.g. poly(oligo(ethylene glycol) methyl ether methacrylate) (POEGMA)). Importantly, the depolymerization product can be utilized to either reconstruct the linear polymer or create an entirely new insoluble gel that can also be subjected to depolymerization. This work expands the potential of polymers made by CRP, pushes the boundaries of depolymerization, offers intriguing mechanistic aspects, and enables new applications.

scholarly journals Nano-Assemblies from Amphiphilic PnBA-b-POEGA Copolymers as Drug Nanocarriers

Polymers ◽  
2021 ◽  
Vol 13 (7) ◽  
pp. 1164
Author(s):  
Angeliki Chroni ◽  
Thomas Mavromoustakos ◽  
Stergios Pispas
Keyword(s):  
Molecular Weight ◽  
Chain Transfer ◽  
Raft Polymerization ◽  
Polymeric Nanocarriers ◽  
Reversible Addition ◽  
2D Noesy ◽  
Drug Nanocarriers ◽  
Glycol Methyl Ether ◽  
Different Molecular Weight

The focus of this study is the development of highly stable losartan potassium (LSR) polymeric nanocarriers. Two novel amphiphilic poly(n-butyl acrylate)-block-poly(oligo(ethylene glycol) methyl ether acrylate) (PnBA-b-POEGA) copolymers with different molecular weight (Mw) of PnBA are synthesized via reversible addition fragmentation chain transfer (RAFT) polymerization, followed by the encapsulation of LSR into both PnBA-b-POEGA micelles. Based on dynamic light scattering (DLS), the PnBA30-b-POEGA70 and PnBA27-b-POEGA73 (where the subscripts denote wt.% composition of the components) copolymers formed micelles of 10 nm and 24 nm in water. The LSR-loaded PnBA-b-POEGA nanocarriers presented increased size and greater mass nanostructures compared to empty micelles, implying the successful loading of LSR into the inner hydrophobic domains. A thorough NMR (nuclear magnetic resonance) characterization of the LSR-loaded PnBA-b-POEGA nanocarriers was conducted. Strong intermolecular interactions between the biphenyl ring and the butyl chain of LSR with the methylene signals of PnBA were evidenced by 2D-NOESY experiments. The highest hydrophobicity of the PnBA27-b-POEGA73 micelles contributed to an efficient encapsulation of LSR into the micelles exhibiting a greater value of %EE compared to PnBA30-b-POEGA70 + 50% LSR nanocarriers. Ultrasound release profiles of LSR signified that a great amount of the encapsulated LSR is strongly attached to both PnBA30-b-POEGA70 and PnBA27-b-POEGA73 micelles.

scholarly journals Reversible addition fragmentation chain transfer polymerization - RAFT

2004 ◽  
Vol 58 (11) ◽  
pp. 514-520
Author(s):  
Milena Avramovic ◽  
Lynne Katsikas ◽  
Branko Dunjic ◽  
Ivanka Popovic
Keyword(s):  
Radical Polymerization ◽  
Chain Transfer ◽  
Raft Polymerization ◽  
General Structure ◽  
Controlled Radical Polymerization ◽  
Molecular Structures ◽  
Reversible Addition ◽  
Chain Transfer Polymerization

The fundamentals of controlled radical polymerization are presented in this review. The paper focuses on reversible addition fragmentation chain transfer (RAFT) polymerization. The mechanism and specifics of this type of polymerization are discussed, as are the possibilities of synthesizing complex macro-molecular structures. The synthesis and properties of RAFT agents, of the general structure Z-C(=S)-S-R, are presented.

RAFT Polymerization of Monomers with Highly Disparate Reactivities: Use of a Single RAFT Agent and the Synthesis of Poly(styrene-block-vinyl acetate)

2013 ◽  
Vol 66 (12) ◽  
pp. 1564 ◽  
Author(s):  
Lily A. Dayter ◽  
Kate A. Murphy ◽  
Devon A. Shipp
Keyword(s):  
Block Copolymers ◽  
Vinyl Acetate ◽  
Chain Transfer ◽  
Raft Polymerization ◽  
Good Control ◽  
Scanning Calorimetry ◽  
Styrene Polymerization ◽  
Reversible Addition ◽  
Raft Agent ◽  
End Group

A single reversible addition–fragmentation chain transfer (RAFT) agent, malonate N,N-diphenyldithiocarbamate (MDP-DTC) is shown to successfully mediate the polymerization of several monomers with greatly differing reactivities in radical/RAFT polymerizations, including both vinyl acetate and styrene. The chain transfer constants (Ctr) for MDP-DTC for both these monomers were evaluated; these were found to be ~2.7 in styrene and ~26 in vinyl acetate, indicating moderate control over styrene polymerization and good control of vinyl acetate polymerization. In particular, the MDP-DTC RAFT agent allowed for the synthesis of block copolymers of these two monomers without the need for protonation/deprotonation switching, as has been previously developed with N-(4-pyridinyl)-N-methyldithiocarbamate RAFT agents, or other end-group transformations. The thermal properties of the block copolymers were studied using differential scanning calorimetry, and those with sufficiently high molecular weight and styrene composition appear to undergo phase separation. Thus, MDP-DTC may be useful for the production of other block copolymers consisting of monomers with highly dissimilar reactivities.

scholarly journals Fundamentals of reversible addition–fragmentation chain transfer (RAFT)

2020 ◽  
Vol 0 (0) ◽  
Author(s):  
Catherine L. Moad ◽  
Graeme Moad
Keyword(s):  
Radical Polymerization ◽  
Chain Length ◽  
Molar Mass ◽  
Chain Transfer ◽  
Raft Polymerization ◽  
Length Distribution ◽  
Chain Length Distribution ◽  
Reversible Addition ◽  
Raft Agent ◽  
End Group

Abstract Radical polymerization is transformed into what is known as reversible addition–fragmentation chain transfer (RAFT) polymerization by the addition of a RAFT agent. RAFT polymerization enables the preparation of polymers with predictable molar mass, narrow chain length distribution, high end-group integrity and provides the ability to construct macromolecules with the intricate architectures and composition demanded by modern applications in medicine, electronics and nanotechnology. This paper provides a background to understanding the mechanism of RAFT polymerization and how this technique has evolved.

scholarly journals Living Radical Polymerization by the RAFT Process - A Second Update

2009 ◽  
Vol 62 (11) ◽  
pp. 1402 ◽  
Author(s):  
Graeme Moad ◽  
Ezio Rizzardo ◽  
San H. Thang
Keyword(s):  
Radical Polymerization ◽  
Chain Transfer ◽  
Raft Polymerization ◽  
Diverse Range ◽  
Reversible Addition ◽  
Reversible Deactivation ◽  
Modified Surfaces ◽  
Diagnostic Applications ◽  
Reversible Deactivation Radical Polymerization ◽  
End Group

This paper provides a second update to the review of reversible deactivation radical polymerization achieved with thiocarbonylthio compounds (ZC(=S)SR) by a mechanism of reversible addition–fragmentation chain transfer (RAFT) that was published in June 2005 (Aust. J. Chem. 2005, 58, 379–410). The first update was published in November 2006 (Aust. J. Chem. 2006, 59, 669–692). This review cites over 500 papers that appeared during the period mid-2006 to mid-2009 covering various aspects of RAFT polymerization ranging from reagent synthesis and properties, kinetics and mechanism of polymerization, novel polymer syntheses and a diverse range of applications. Significant developments have occurred, particularly in the areas of novel RAFT agents, techniques for end-group removal and transformation, the production of micro/nanoparticles and modified surfaces, and biopolymer conjugates both for therapeutic and diagnostic applications.

Synthesis of N-vinylcarbazole–N-vinylpyrrolidone amphiphilic block copolymers by xanthate-mediated controlled radical polymerization

2010 ◽  
Vol 88 (3) ◽  
pp. 228-235 ◽  
Author(s):  
Chih-Feng Huang ◽  
Jeong Ae Yoon ◽  
Krzysztof Matyjaszewski
Keyword(s):  
Block Copolymers ◽  
Chain Transfer ◽  
Raft Polymerization ◽  
Controlled Radical Polymerization ◽  
Amphiphilic Block Copolymers ◽  
Force Microscopy ◽  
Molecular Weights ◽  
Atomic Force ◽  
Reversible Addition ◽  
Mode Atomic Force Microscopy

Amphiphilic block copolymers poly(N-vinylcarbazole)-b-poly(N-vinylpyrrolidone) (PNVK-b-PNVP) were prepared by xanthate-mediated reversible addition-fragmentation chain transfer (RAFT) polymerization. Both the PNVK and PNVP macroinitiators and the resulting block copolymers had molecular weights close to theoretical values, predicted for efficient initiation, in the range of Mn = 30 000 to 90 000. The block copolymers dissolved in several organic solvents but, depending on their composition, in methanol formed either micelles or large aggregates, as confirmed by dynamic light scattering. The presence of globular aggregates was confirmed by tapping mode atomic force microscopy.

A Novel One-Pot Procedure for the Fast and Efficient Conversion of RAFT Polymers into Hydroxy-Functional Polymers

2009 ◽  
Vol 62 (8) ◽  
pp. 806 ◽  
Author(s):  
Till Gruendling ◽  
Mathias Dietrich ◽  
Christopher Barner-Kowollik
Keyword(s):  
Elevated Temperatures ◽  
Raft Polymerization ◽  
Functional Polymers ◽  
Size Exclusion ◽  
One Pot ◽  
Reversible Addition ◽  
Exclusion Chromatography ◽  
Azo Initiator ◽  
Raft Polymers ◽  
End Group

We report on the successful quantitative transformation of methacrylate and acrylate-type polymers prepared by reversible addition–fragmentation chain transfer (RAFT) polymerization carrying a dithioester-end-group into hydroxy-functional polymers. The simple reaction procedure involves stirring a solution of the dithioester-capped polymer and an azo-initiator in tetrahydrofuran at elevated temperatures (T = 60°C) in the presence of air. This reaction quantitatively yields hydroperoxide functionalities that can be efficiently reduced to hydroxy groups in a one-pot procedure using triphenylphosphine. Size exclusion chromatography–electrospray mass spectrometry was employed to monitor the progress of the reaction. The new backbone-linked hydroxy group provides a versatile anchor for chemical end-group conversions and conjugation reactions with prepared RAFT polymers, which alleviates problems with the rather limited ability of the dithioester-end-group to undergo non-radical transformations.

scholarly journals Living Radical Polymerization by the RAFT Process – A Third Update

2012 ◽  
Vol 65 (8) ◽  
pp. 985 ◽  
Author(s):  
Graeme Moad ◽  
Ezio Rizzardo ◽  
San H. Thang
Keyword(s):  
Radical Polymerization ◽  
Chain Transfer ◽  
Raft Polymerization ◽  
Diverse Range ◽  
Reversible Addition ◽  
Reversible Deactivation ◽  
Modified Surfaces ◽  
Diagnostic Applications ◽  
Reversible Deactivation Radical Polymerization ◽  
End Group

This paper provides a third update to the review of reversible deactivation radical polymerization (RDRP) achieved with thiocarbonylthio compounds (ZC(=S)SR) by a mechanism of reversible addition-fragmentation chain transfer (RAFT) that was published in June 2005 (Aust. J. Chem. 2005, 58, 379). The first update was published in November 2006 (Aust. J. Chem. 2006, 59, 669) and the second in December 2009 (Aust. J. Chem. 2009, 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.

Reversible Addition-Fragmentation Chain Transfer (RAFT) Polymerization of Vinyl Monomers Initiated by Poly(methyl methacrylate) Peroxide

e-Polymers ◽  
2007 ◽  
Vol 7 (1) ◽  
Author(s):  
Zhengbiao Zhang ◽  
Xiulin Zhu ◽  
Jian Zhu ◽  
Zhenping Cheng
Keyword(s):  
Methyl Methacrylate ◽  
Chain Transfer ◽  
Raft Polymerization ◽  
Controlled Radical Polymerization ◽  
Polymer Chains ◽  
Poly Methyl Methacrylate ◽  
Molecular Weights ◽  
H Nmr ◽  
Reversible Addition ◽  
Living Controlled Radical Polymerization

AbstractPoly(methyl methacrylate) peroxide (PMMAP) was synthesized and used as the initiator in the reversible addition-fragmentation chain transfer (RAFT) polymerization. Methyl methacrylate (MMA) as the monomer and 2-cyanoprop-2-yl 1-dithionaphthalate (CPDN) as the chain transfer agent was used in the polymerization system. The polymerization was successfully initiated by PMMAP while maintaining features of “living”/controlled radical polymerization such as the number-average molecular weights (Mn) increasing linearly with the monomer conversions and low polydispersity index (PDI) values. The results of 1H NMR and IR spectra confirmed that a small quantity of polymer chains were derived from the PMMAP moieties. The PMMAP can also initiate the RAFT polymerization of styrene (St) and methyl acrylate (MA), and the polymerization proceeded in a “living”/controlled fashion.

Controlled radical polymerization of vinyl ketones using visible light

2017 ◽  
Vol 8 (21) ◽  
pp. 3351-3356 ◽  
Author(s):  
In-Hwan Lee ◽  
Emre H. Discekici ◽  
Athina Anastasaki ◽  
Javier Read de Alaniz ◽  
Craig J. Hawker
Keyword(s):  
Electron Transfer ◽  
Visible Light ◽  
Radical Polymerization ◽  
Photoinduced Electron Transfer ◽  
Chain Transfer ◽  
Raft Polymerization ◽  
Controlled Radical Polymerization ◽  
Eosin Y ◽  
Methyl Ethyl ◽  
Reversible Addition

Herein we report the photoinduced electron transfer–reversible addition–fragmentation chain transfer (PET-RAFT) polymerization of a range of vinyl ketone monomers including methyl, ethyl and phenyl derivatives, using Eosin Y as an organic photoredox catalyst and visible light.

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