Reversible Addition−Fragmentation Chain Transfer (RAFT) Polymerization in an Inverse Microemulsion: Partitioning of Chain Transfer Agent (CTA) and Its Effects on Polymer Molecular Weight§

AbstractHigh molecular weight polystyrene homopolymers with low dispersity were synthesized by a reversible addition-fragmentation chain transfer (RAFT) polymerization method using 0.03 and 0.3 wt% of cumyl dithiobenzoate (CDB) vs. styrene (St) and the azobis(isobutyronitrile) initiator, at the polymerization temperature of 60 or 70 °C. The optimal high molecular weight polystyrene via this synthetic scheme shows Mw = 46.5×104, Mn = 33.3×104, and a dispersity of 1.40. The polystyrene chain contains a dithiobenzoate C=S moiety and thus can be used as a macro-chain-transfer agent for the polymerization of other monomers and for the synthesis of diversified block copolymers under mild conditions. The changes of the polystyrene molecular weight and dispersity were studied by the influences of the initial concentration ratio of CDB to styrene ([CDB]0/[St]0), the polymerization temperature, and the polymerization time. The PS molecular weight is inversely proportional to the [CDB]0/[St]0 ratio. Decreasing CDB from 0.3 to 0.03 wt%, a high MW PS was obtained, while the dispersity was observed to increase from 1.10 to 1.40. The PS molecular weight increases with the increase of the reaction time, while the dispersity of PS varies little from 1.12 to 1.23. The molecular weight and dispersity increase with the increase of the polymerization temperature. As the temperature arises from 60°C to 70°C, the conversion increases considerably from 25.8% to 39.9%, and the dispersity increases slightly from 1.15 to 1.17. As the temperature reaches 80°C, the conversion increases considerably to 64.7%, and the dispersity increases to 1.53. The polymer molecular weight of the polystyrene prepared by the RAFT method is suitable for the applications of engineering materials.

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

Polymers ◽

10.3390/polym13071164 ◽

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.

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Dendrimer-star polymer and block copolymer prepared by reversible addition-fragmentation chain transfer (RAFT) polymerization with dendritic chain transfer agent

Journal of Polymer Science Part A Polymer Chemistry ◽

10.1002/pola.21098 ◽

2005 ◽

Vol 43 (24) ◽

pp. 6379-6393 ◽

Cited By ~ 44

Author(s):

Chun-Yan Hong ◽

Ye-Zi You ◽

Jun Liu ◽

Cai-Yuan Pan

Keyword(s):

Block Copolymer ◽

Chain Transfer ◽

Raft Polymerization ◽

Chain Transfer Agent ◽

Star Polymer ◽

Reversible Addition

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

e-Polymers ◽

10.1515/epoly.2008.8.1.256 ◽

2008 ◽

Vol 8 (1) ◽

Cited By ~ 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.

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Using Reversible Addition-Fragmentation Chain Transfer Polymerization to Synthesize Well-Defined Polymer

Advanced Materials Research ◽

10.4028/www.scientific.net/amr.781-784.415 ◽

2013 ◽

Vol 781-784 ◽

pp. 415-418

Author(s):

Shou Juan Bian ◽

Ying Juan Fu ◽

Meng Hua Qin

Keyword(s):

Molecular Weight ◽

Chain Transfer ◽

Raft Polymerization ◽

Reaction Conditions ◽

Reversible Addition ◽

Complex Architectures ◽

Versatile Tool ◽

Green Polymers ◽

Controlled Structure ◽

Chain Transfer Polymerization

As an effective and versatile tool for production of functional polymer, RAFT polymerization has been successfully applied to the polymerization of block copolymers and other polymers of complex architectures with precisely controlled structure, molecular weight, and polydispersity. It has the ability to control polymerization of most monomers and has fine compatibility with reaction conditions. The present article summarized some of the features of the RAFT process, and reviewed the recent advances in the production of green polymers.

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Role of Lewis Acids in Preventing the Degradation of Dithioester-Dormant Species in the RAFT Polymerization of Acrylamides in Methanol to Enable the Successful Dual Control of Molecular Weight and Tacticity

10.26434/chemrxiv.14622915 ◽

2021 ◽

Author(s):

Yuji Imamura ◽

Shigeru Yamago

Keyword(s):

Molecular Weight ◽

Lewis Acids ◽

Chain Transfer ◽

Raft Polymerization ◽

Degradation Mechanism ◽

Earth Metal ◽

Nucleophilic Attack ◽

Molecular Weights ◽

Reversible Addition ◽

Metal Triflates

Reversible addition-fragmentation chain transfer (RAFT) polymerization of acrylamide in methanol using dithioester RAFT chain-transfer agents was unsuccessful due to degradation of the end group. However, this degradation was completely suppressed by the addition of rare-earth metal triflates (RMTs). As RMTs are effective for the stereoselective polymerization of acrylamides, RAFT polymerization in the presence of RMTs afforded the corresponding poly(acrylamide)s with controlled molecular weight and tacticity. The conditions allowed the synthesis of high-molecular-weight polyacrylamides with molecular weights up to 168,000, low dispersity (<1.5) and high tacticity (90% <i>meso</i> diad selectivity). The degradation mechanism initiated by nucleophilic attack of acrylamide on the dithioester group was experimentally clarified for the first time. As RMT is a Lewis acid, its coordination to the amide group of acrylamide reduces its nucleophilicity.

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Role of Lewis Acids in Preventing the Degradation of Dithioester-Dormant Species in the RAFT Polymerization of Acrylamides in Methanol to Enable the Successful Dual Control of Molecular Weight and Tacticity

10.26434/chemrxiv.14622915.v1 ◽

2021 ◽

Author(s):

Yuji Imamura ◽

Shigeru Yamago

Keyword(s):

Molecular Weight ◽

Lewis Acids ◽

Chain Transfer ◽

Raft Polymerization ◽

Degradation Mechanism ◽

Earth Metal ◽

Nucleophilic Attack ◽

Molecular Weights ◽

Reversible Addition ◽

Metal Triflates

Reversible addition-fragmentation chain transfer (RAFT) polymerization of acrylamide in methanol using dithioester RAFT chain-transfer agents was unsuccessful due to degradation of the end group. However, this degradation was completely suppressed by the addition of rare-earth metal triflates (RMTs). As RMTs are effective for the stereoselective polymerization of acrylamides, RAFT polymerization in the presence of RMTs afforded the corresponding poly(acrylamide)s with controlled molecular weight and tacticity. The conditions allowed the synthesis of high-molecular-weight polyacrylamides with molecular weights up to 168,000, low dispersity (<1.5) and high tacticity (90% <i>meso</i> diad selectivity). The degradation mechanism initiated by nucleophilic attack of acrylamide on the dithioester group was experimentally clarified for the first time. As RMT is a Lewis acid, its coordination to the amide group of acrylamide reduces its nucleophilicity.

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RAFT Polymerization of 2,2,3,3-Tetrafluoropropyl Methacrylate in the Presence of Lewis Acids

Key Engineering Materials ◽

10.4028/www.scientific.net/kem.899.525 ◽

2021 ◽

Vol 899 ◽

pp. 525-531

Author(s):

Oleg A. Lebedev ◽

Alexandra O. Grigoreva ◽

Sergey D. Zaitsev

Keyword(s):

Polymer Chain ◽

Lewis Acids ◽

Chain Transfer ◽

Raft Polymerization ◽

Point Of View ◽

Chain Transfer Agent ◽

Reversible Addition

The influence of various tacticity regulators on the reversible addition-fragmentation (RAFT) polymerization of 2,2,3,3-tetrafluoropropyl methacrylate in the presence of 2-cyano-2-propyldodecyltritiocarbonate as an chain transfer agent was investigated. Among Lewis acids considered, the polymerization of TFPMA in dioxane with ZnBr2 turned out to be the most effective from the point of view of tacticity; the polymer with the highest isotacticity is formed. The addition of hexafluoroisopropanol leads to an increase in the heterotacticity and a decrease in the isotacticity of the polymer chain.

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Synthesis and Investigation of pH-Switchable RAFT Agent in Polymerization of Styrene

Key Engineering Materials ◽

10.4028/www.scientific.net/kem.899.638 ◽

2021 ◽

Vol 899 ◽

pp. 638-643

Author(s):

Artem Vlasov ◽

Alexandra O. Grigoreva ◽

Sergey D. Zaitsev

Keyword(s):

Mass Distribution ◽

Molar Mass ◽

Chain Transfer ◽

Raft Polymerization ◽

Chain Transfer Agent ◽

Molar Mass Distribution ◽

Reversible Addition ◽

Raft Agent ◽

Kinetic Features

pH-switchable chain transfer agent 1-cyano-1-methylethyl (phenyl)(pyridin-4-yl)-carbamodithioate (CMPC) was synthesized and reversible addition-fragmentation chain-transfer (RAFT) polymerization of styrene in presence of CMPC was studied. It was shown that presence of CMPC affects molar mass distribution and kinetic features and realizes supposed mechanism of RAFT polymerization. Different effect of CMPC on polymerization of styrene in presence of protic acids was studied.

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Synthesis of azobenzene-centered (co)polymers via reversible addition-fragmentation chain transfer (RAFT) polymerization

e-Polymers ◽

10.1515/epoly.2007.7.1.1059 ◽

2007 ◽

Vol 7 (1) ◽

Author(s):

Yu Liping ◽

Zhu Jian ◽

Cheng Zhenping ◽

Zhang Zhengbiao ◽

Zhang Wei ◽

...

Keyword(s):

Molecular Weight ◽

Chain Transfer ◽

Raft Polymerization ◽

Gel Permeation Chromatography ◽

Polymer Chains ◽

Dimethyl Formamide ◽

Reversible Addition ◽

Raft Agent ◽

Pentablock Copolymers ◽

Ft Ir

Abstract An azobenzene-based dithiocarbamate, 4,4'-bis[2-(carbazole-N-dithio formatyl)-2-methyl-propionatyl]-azobenzene (CDMPA), was synthesized and used as the chain transfer agent (CTA) for reversible addition-fragmentation chain transfer (RAFT) polymerization of styrene in anisole solution. Well-defined azobenzene-centered and carbazole-ended polystyrene (PS) with well-controlled molecular weight (Mn) and narrow molecular weight distributions (Mw/Mn) was obtained. The good agreement between the theoretical molecular weight (Mn,th) and the 1H NMR determined molecular weight (Mn,NMR) indicated that most of the polymer chains contained an azo-functional center-group end-capped with the carbazole moieties, which were derived from the RAFT agent. The obtained polystyrene (PS) showed a strong ultraviolet absorption in tetrahydrofuran (THF) and emitted fluorescence after excited by UV-irradiation in N,N’-dimethyl formamide (DMF) solutions. The PS was used as the macro-RAFT agent to carry out the polymerization of methyl acrylate (MA) and N-isopropylacrylamide (NIPAAM). Triblock copolymers (PMA-b-PS-b-PMA), and pentablock copolymers (PNIPAAM-b-PMA-b-PS-b-PMA-b-PNIPAAM) were obtained, respectively. These copolymers were characterized by gel permeation chromatography (GPC), FT-IR spectroscopy and NMR spectroscopy.

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