scholarly journals Synthesis of Poly(3-vinylpyridine)-Block-Polystyrene Diblock Copolymers via Surfactant-Free RAFT Emulsion Polymerization

Materials ◽  
2019 ◽  
Vol 12 (19) ◽  
pp. 3145 ◽  
Author(s):  
Katharina Nieswandt ◽  
Prokopios Georgopanos ◽  
Clarissa Abetz ◽  
Volkan Filiz ◽  
Volker Abetz
Keyword(s):  
Emulsion Polymerization ◽  
Self Assembly ◽  
Diblock Copolymers ◽  
Chain Transfer ◽  
Raft Polymerization ◽  
Free Water ◽  
Monomer Conversion ◽  
Molecular Weights ◽  
Reversible Addition

In this work, we present a novel synthetic route to diblock copolymers based on styrene and 3-vinylpyridine monomers. Surfactant-free water-based reversible addition–fragmentation chain transfer (RAFT) emulsion polymerization of styrene in the presence of the macroRAFT agent poly(3-vinylpyridine) (P3VP) is used to synthesize diblock copolymers with molecular weights of around 60 kDa. The proposed mechanism for the poly(3-vinylpyridine)-block-poly(styrene) (P3VP-b-PS) synthesis is the polymerization-induced self-assembly (PISA) which involves the in situ formation of well-defined micellar nanoscale objects consisting of a PS core and a stabilizing P3VP macroRAFT agent corona. The presented approach shows a well-controlled RAFT polymerization, allowing for the synthesis of diblock copolymers with high monomer conversion. The obtained diblock copolymers display microphase-separated structures according to their composition.

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.

scholarly journals Redox-Initiated Reversible Addition–Fragmentation Chain Transfer (RAFT) Polymerization

2019 ◽  
Vol 72 (7) ◽  
pp. 479 ◽  
Author(s):  
Amin Reyhani ◽  
Thomas G. McKenzie ◽  
Qiang Fu ◽  
Greg G. Qiao
Keyword(s):  
Redox Reactions ◽  
Chain Transfer ◽  
Raft Polymerization ◽  
Molecular Structures ◽  
Biologically Relevant ◽  
Molecular Weights ◽  
Polymeric Biomaterials ◽  
Reversible Addition ◽  
Wide Range ◽  
Metal Catalyzed

Reversible addition–fragmentation chain transfer (RAFT) polymerization initiated by a radical-forming redox reaction between a reducing and an oxidizing agent (i.e. ‘redox RAFT’) represents a simple, versatile, and highly useful platform for controlled polymer synthesis. Herein, the potency of a wide range of redox initiation systems including enzyme-mediated redox reactions, the Fenton reaction, peroxide-based reactions, and metal-catalyzed redox reactions, and their application in initiating RAFT polymerization, are reviewed. These redox-RAFT polymerization methods have been widely studied for synthesizing a broad range of homo- and co-polymers with tailored molecular weights, compositions, and (macro)molecular structures. It has been demonstrated that redox-RAFT polymerization holds particular promise due to its excellent performance under mild conditions, typically operating at room temperature. Redox-RAFT polymerization is therefore an important and core part of the RAFT methodology handbook and may be of particular importance going forward for the fabrication of polymeric biomaterials under biologically relevant conditions or in biological systems, in which naturally occurring redox reactions are prevalent.

RAFT Graft Polymerization of 2-(Dimethylaminoethyl) Methacrylate onto Cellulose Fibre

2006 ◽  
Vol 59 (10) ◽  
pp. 737 ◽  
Author(s):  
Debashish Roy ◽  
James T. Guthrie ◽  
Sébastien Perrier
Keyword(s):  
Graft Polymerization ◽  
Chain Transfer ◽  
Raft Polymerization ◽  
Cellulose Fibre ◽  
Monomer Conversion ◽  
Living System ◽  
Degree Of Polymerization ◽  
Polymerization Time ◽  
Grafted Polymer ◽  
Reversible Addition

Poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) was grafted from cellulose by reversible addition–fragmentation chain transfer (RAFT) polymerization. The use of a free chain transfer agent in solution allowed for a better control over graft ratio, chain length of grafted polymer, monomer conversion, and homopolymer formation in solution. An increase in polymerization time or degree of polymerization led to an increase in graft ratio, as expected from a living system.

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.

scholarly journals A well-defined polyelectrolyte and its copolymers by reversible addition fragmentation chain transfer (RAFT) polymerization: synthesis and applications

RSC Advances ◽  
2015 ◽  
Vol 5 (119) ◽  
pp. 98559-98565 ◽  
Author(s):  
Muhammad Mumtaz ◽  
Karim Aissou ◽  
Dimitrios Katsigiannopoulos ◽  
Cyril Brochon ◽  
Eric Cloutet ◽  
...  
Keyword(s):  
Block Copolymer ◽  
Self Assembly ◽  
Chain Transfer ◽  
Raft Polymerization ◽  
Controlled Polymerization ◽  
Reversible Addition ◽  
Block Copolymer Electrolytes

Controlled polymerization and self-assembly of novel block copolymer electrolytes.

scholarly journals Experimental Design in Polymer Chemistry—A Guide towards True Optimization of a RAFT Polymerization Using Design of Experiments (DoE)

Polymers ◽  
2021 ◽  
Vol 13 (18) ◽  
pp. 3147
Author(s):  
Tilman Eckert ◽  
Florian C. Klein ◽  
Piet Frieler ◽  
Oliver Thunich ◽  
Volker Abetz
Keyword(s):  
Design Of Experiments ◽  
Prediction Models ◽  
Information Gain ◽  
Raft Polymerization ◽  
Academic Research ◽  
Monomer Conversion ◽  
Individual Response ◽  
Molecular Weights ◽  
Reversible Addition ◽  
Face Centered

Despite the great potential of design of experiments (DoE) for efficiency and plannability in academic research, it remains a method predominantly used in industrial processes. From our perspective though, DoE additionally provides greater information gain than conventional experimentation approaches, even for more complex systems such as chemical reactions. Hence, this work presents a comprehensive DoE investigation on thermally initiated reversible addition–fragmentation chain transfer (RAFT) polymerization of methacrylamide (MAAm). To facilitate the adaptation of DoE for virtually every other polymerization, this work provides a step-by-step application guide emphasizing the biggest challenges along the way. Optimization of the RAFT system was achieved via response surface methodology utilizing a face-centered central composite design (FC-CCD). Highly accurate prediction models for the responses of monomer conversion, theoretical and apparent number averaged molecular weights, and dispersity are presented. The obtained equations not only facilitate thorough understanding of the observed system but also allow selection of synthetic targets for each individual response by prediction of the respective optimal factor settings. This work successfully demonstrates the great capability of DoE in academic research and aims to encourage fellow scientists to incorporate the technique into their repertoire of experimental strategies.

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.

Room temperature synthesis of block copolymer nano-objects with different morphologies via ultrasound initiated RAFT polymerization-induced self-assembly (sono-RAFT-PISA)

2020 ◽  
Vol 11 (21) ◽  
pp. 3564-3572
Author(s):  
Jing Wan ◽  
Bo Fan ◽  
Yiyi Liu ◽  
Tina Hsia ◽  
Kaiyuan Qin ◽  
...  
Keyword(s):  
Block Copolymer ◽  
Self Assembly ◽  
Room Temperature ◽  
Chain Transfer ◽  
Raft Polymerization ◽  
Aqueous System ◽  
Temperature Synthesis ◽  
Room Temperature Synthesis ◽  
System P ◽  
Reversible Addition

The first room temperature synthesis of diblock copolymer nano-objects with different morphologies using ultrasound (990 kHz) initiated reversible addition-fragmentation chain transfer PISA (sono-RAFT-PISA) in aqueous system.

Synthesis, self-assembly and self-healing properties of organic–inorganic ABA triblock copolymers with poly(POSS acrylate) endblocks

2019 ◽  
Vol 10 (19) ◽  
pp. 2424-2435 ◽  
Author(s):  
Bingjie Zhao ◽  
Sen Xu ◽  
Sixun Zheng
Keyword(s):  
Self Assembly ◽  
Triblock Copolymer ◽  
Chain Transfer ◽  
Triblock Copolymers ◽  
Raft Polymerization ◽  
Self Healing ◽  
Reversible Addition ◽  
Aba Triblock Copolymer

A novel organic–inorganic ABA triblock copolymer with a poly(acrylate amide) (PAA) midblock and poly(POSS acrylate) [P(POSS)] endblocks was synthesized via sequential reversible addition–fragmentation chain transfer (RAFT) polymerization.

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