Synergistic Interaction Between ATRP and RAFT: Taking the Best of Each World

2009 ◽  
Vol 62 (11) ◽  
pp. 1384 ◽  
Author(s):  
Yungwan Kwak ◽  
Renaud Nicolaÿ ◽  
Krzysztof Matyjaszewski
Keyword(s):  
Chain Transfer ◽  
Raft Polymerization ◽  
Atom Transfer ◽  
Step Method ◽  
One Pot ◽  
Reversible Addition ◽  
Raft Agent ◽  
Recent Developments ◽  
One Step ◽  
Leaving Groups

This review covers recent developments on the combination of atom transfer radical polymerization (ATRP) and reversible addition–fragmentation chain transfer (RAFT) polymerization to produce well controlled (co)polymers. This review discusses the relative reactivity of the R group in ATRP and RAFT, provides a comparison of dithiocarbamate (DC), trithiocarbonate (TTC), dithioester (DTE), and xanthate versus bromine or chlorine, and an optimization of catalyst/ligand selection. The level of control in iniferter polymerization with DC was greatly improved by the addition of a copper complex. New TTC inifers with bromopropionate and bromoisobutyrate groups have been prepared to conduct, concurrently or sequentially, ATRP from Br-end groups, ATRP from the TTC moiety, and RAFT polymerization from the TTC moiety, depending on the combination of monomer and catalyst employed in the reaction. The use of concurrent ATRP/RAFT (or copper-catalyzed RAFT polymerization or ATRP with dithioester leaving groups), resulted in improved control over the synthesis of homo- and block (co)polymers and allowed preparation of well-defined high-molecular-weight polymers exceeding 1 million. Block copolymers that could not be prepared previously have been synthesized by sequential ATRP and RAFT polymerization using a bromoxanthate inifer. A simple, versatile, and one-step method involving atom-transfer radical addition–fragmentation (ATRAF) for the preparation of various chain transfer agents (including DC, DTE, and xanthate) in high purity is discussed and a one-pot, two-step polymerization starting with a RAFT agent synthesized by ATRAF, followed by polymerization, is demonstrated.

One-pot polymer brush synthesis via simultaneous isocyanate coupling chemistry and “grafting from” RAFT polymerization

2014 ◽  
Vol 5 (8) ◽  
pp. 2816-2823 ◽  
Author(s):  
S. P. Le-Masurier ◽  
G. Gody ◽  
S. Perrier ◽  
A. M. Granville
Keyword(s):  
Chain Transfer ◽  
Raft Polymerization ◽  
Polymer Brush ◽  
One Pot ◽  
Reversible Addition ◽  
Raft Agent ◽  
Grafting From

One-pot ‘grafting from’ of polystyrene on polydopamine particles was investigated using a newly developed carbonyl-azide reversible addition–fragmentation chain transfer (RAFT) agent.

Synthesis and characterization of a naphthalimide–dye end-labeled copolymer by reversible addition–fragmentation chain transfer (RAFT) polymerization

2011 ◽  
Vol 89 (3) ◽  
pp. 317-325 ◽  
Author(s):  
Binxin Li ◽  
Daniel Majonis ◽  
Peng Liu ◽  
Mitchell A. Winnik
Keyword(s):  
Chain Transfer ◽  
Raft Polymerization ◽  
Polymer Composition ◽  
Cooh Group ◽  
Agent Based ◽  
Molecular Weights ◽  
Reversible Addition ◽  
Raft Agent ◽  
End Use ◽  
Naphthalimide Dye

We describe the synthesis of an end-functionalized copolymer of N-(2-hydroxypropyl)methacrylamide (HPMA) and N-hydroxysuccinimide methacrylate (NMS) by reversible addition–fragmentation chain transfer (RAFT) polymerization. To control the polymer composition, the faster reacting monomer (NMS) was added slowly to the reaction mixture beginning 30 min after initating the polymerization (ca. 16% HPMA conversion). One RAFT agent, based on azocyanopentanoic acid, introduced a –COOH group to the chain at one end. Use of a different RAFT agent containing a 4-amino-1,8-naphthalimide dye introduced a UV–vis absorbing and fluorescent group at this chain end. The polymers obtained had molecular weights of 30 000 and 20 000, respectively, and contained about 30 mol% NMS active ester groups.

Controlled/Living Radical Polymerization of Semifluorinated (Meth)acrylates

Synlett ◽  
2018 ◽  
Vol 29 (12) ◽  
pp. 1543-1551 ◽  
Author(s):  
Mao Chen ◽  
Honghong Gong ◽  
Yu Gu
Keyword(s):  
Atom Transfer Radical Polymerization ◽  
Radical Polymerization ◽  
Chain Transfer ◽  
Raft Polymerization ◽  
Living Radical Polymerization ◽  
Atom Transfer ◽  
Reversible Addition ◽  
Controlled Living Radical Polymerization ◽  
Chain Transfer Polymerization ◽  
Semifluorinated Polymers

Fluorinated polymers are important materials for applications in many areas. This article summarizes the development of controlled/living radical polymerization (CRP) of semifluorinated (meth)acrylates, and briefly introduces their reaction mechanisms. While the classical CRP such as atom transfer radical polymerization (ATRP), reversible addition-fragmentation chain transfer (RAFT) polymerization and nitroxide-mediated radical polymerization (NMP) have promoted the preparation of semifluorinated polymers with tailor-designed architectures, recent development of photo-CRP has led to unprecedented accuracy and monomer scope. We expect that synthetic advances will facilitate the engineering of advanced fluorinated materials with unique properties.1 Introduction2 Atom Transfer Radical Polymerization3 Reversible Addition-Fragmentation Chain Transfer Polymerization4 Nitroxide-Mediated Radical Polymerization5 Photo-CRP Mediated with Metal Complexes6 Metal-free Photo-CRP7 Conclusion

scholarly journals Synthesis and characterization of triphenylamine and Bbis(indolyl)methane center-functionalized polymer via reversible addition-fragmentation chain transfer polymerization

e-Polymers ◽  
2008 ◽  
Vol 8 (1) ◽  
Author(s):  
Jie Xu ◽  
Wei Shang ◽  
Jian Zhu ◽  
Zhenping Cheng ◽  
Nianchen Zhou ◽  
...  
Keyword(s):  
Molecular Weight ◽  
Chain Transfer ◽  
Raft Polymerization ◽  
Chloroform Solution ◽  
Monomer Conversion ◽  
Benzyl Ester ◽  
Chain Extension ◽  
Reversible Addition ◽  
Raft Agent ◽  
Cyclic Voltammetry Method

AbstractA novel bis-functional reversible addition-fragmentation chain transfer (RAFT) agent bearing triphenylamine (TPA) and bis(indolyl)methane (BIM) groups, {4-[bis(1-carbodithioic acid benzyl ester-indol-3-yl)methyl]phenyl}diphenylamine (BCIMPDPA), was synthesized and successfully used as the RAFT agent to mediate the polymerization of styrene (St). The polymerization results showed that reversible addition-fragmentation chain transfer (RAFT) polymerization of St could be well controlled. The kinetic plot showed it was of first order and the numberaverage molecular weight (Mn(GPC)) of the polymer measured by GPC increased linearly with monomer conversion, simultaneously, the molecular weight distribution of the polymer was also relatively narrow. In addition, the existence of the TPA and BIM groups in the middle of polymer chain was confirmed by chain extension reaction and 1H NMR spectrum. The optical properties of the functionalized polystyrene (PS) in chloroform solution were also investigated. Furthermore, the redox process of the RAFT agent and the functionalized PS were studied by cyclic voltammetry method.

Investigation into the Initialization Behaviour of RAFT-Mediated Styrene–Maleic Anhydride Copolymerizations

2006 ◽  
Vol 59 (10) ◽  
pp. 742 ◽  
Author(s):  
Eric T. A. van den Dungen ◽  
Jacques Rinquest ◽  
Nadine O. Pretorius ◽  
Jean M. McKenzie ◽  
James B. McLeary ◽  
...  
Keyword(s):  
Maleic Anhydride ◽  
Raft Polymerization ◽  
Polymerization Process ◽  
Unit Model ◽  
Reversible Addition ◽  
Raft Agent ◽  
Addition Rate ◽  
Leaving Groups ◽  
Chain Lengths ◽  
Alternating Copolymerization

The living radical alternating copolymerization of styrene and maleic anhydride mediated by the reversible addition–fragmentation chain transfer (RAFT) polymerization process has been studied at short chain lengths using two different dithiobenzoate RAFT agents. The results indicate specificity of addition of the RAFT-agent leaving groups for either styrene or maleic anhydride. The addition rate of the monomers and the fact that monomers are added individually favour the penultimate unit model of polymer propagation.

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.

Reversible addition fragmentation chain transfer (RAFT) polymerization of styrene in fluid CO2

e-Polymers ◽  
2004 ◽  
Vol 4 (1) ◽  
Author(s):  
Toshihiko Arita ◽  
Sabine Beuermann ◽  
Michael Buback ◽  
Philipp Vana
Keyword(s):  
Chain Transfer ◽  
Raft Polymerization ◽  
Molecular Weights ◽  
Reversible Addition ◽  
Significant Difference ◽  
Raft Agent ◽  
Successful Control ◽  
A Minor ◽  
Peak Widths

Abstract Reversible addition fragmentation chain transfer (RAFT) polymerizations of styrene in fluid CO2 have been carried out at 80°C and 300 bar using cumyl dithiobenzoate as the controlling agent in the concentration range of 3.5·10-3 to 2.1·10-2 mol/L. This is the first report on RAFT polymerization in fluid CO2. The polymerization rates were retarded depending on the employed RAFT agent concentration with no significant difference between the RAFT polymerization performed in fluid CO2 and in toluene. Full chain length distributions were analyzed with respect to peak molecular weights, indicating the successful control of radical polymerization in fluid CO2. A characterization of the peak widths may suggest a minor influence of fluid CO2 on the addition reaction of macroradicals on the dithiobenzoate group.

Synthetic Polyampholytes Based Cryoprotective Agents by Reversible Addition Fragmentation Chain Transfer Polymerisation

2013 ◽  
Vol 1499 ◽  
Author(s):  
Robin Rajan ◽  
Kazuaki Matsumura
Keyword(s):  
Chain Transfer ◽  
High Efficiency ◽  
Raft Polymerization ◽  
Freezing And Thawing ◽  
Cryoprotective Agents ◽  
Reversible Addition ◽  
Raft Agent ◽  
High Cytotoxicity ◽  
Methylpropionic Acid ◽  
Polymerization Method

ABSTRACTDimethyl sulfoxide (DMSO) and several naturally occurring polyols or their derivatives (like glycerol) have been used as cryoprotective agents (CPAs) for many years. However DMSO shows high cytotoxicity and affects differentiation of cells, so it needs to be removed immediately after thawing, whereas polyols are comparatively weaker cryoprotective agents. Furthermore, some types of cells are extremely sensitive to damage during freezing and thawing, so cannot be cryopreserved properly using current CPAs. So there is a great need to develop newer cryoprotective agents with lower cytotoxicity and high efficiency for many biological and medical purposes.Recently we showed that carboxylated poly-L-lysine, which is classified as a polyampholyte, has a cryoprotective effect on cells in solution without any other cryoprotectant. Polyampholytes are charged polymers with both positively and negatively charged groups.Therefore, in this research, we are developing a completely synthetic polyampholytes by radical polymerization and will try to elucidate the key parameters of cryoprotective properties. Here we chose reversible addition fragmentation chain transfer (RAFT) polymerization as the mode of polymerization as it is a kind of living polymerization method and can give control over the molecular weight and composition of the copolymer. We evaluated the livingness of the 1:1 copolymer with methacrylic acid (MAA) and 2-Dimethylamino ethyl methacrylate (DMAEMA) with 2-(Dodecylthiocarbonothioylthio)-2-methylpropionic acid as the RAFT agent and the polymer solution showed good cell viability of L929 cells after cryopreservation at 15% copolymer concentration.

Sign in / Sign up

Export Citation Format

Share Document