Controlled radical copolymerization of styrene and maleic anhydride and the synthesis of novel polyolefin-based block copolymers by reversible addition-fragmentation chain-transfer (RAFT) polymerization

2000 ◽  
Vol 38 (19) ◽  
pp. 3596-3603 ◽  
Author(s):  
Hans De Brouwer ◽  
Mike A. J. Schellekens ◽  
Bert Klumperman ◽  
Michael J. Monteiro ◽  
Anton L. German
Keyword(s):  
Block Copolymers ◽  
Maleic Anhydride ◽  
Chain Transfer ◽  
Raft Polymerization ◽  
Radical Copolymerization ◽  
Reversible Addition

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 Synthesis of Terpyridine-Terminated Amphiphilic Block Copolymers and Their Self-Assembly into Metallo-Polymer Nanovesicles

Materials ◽  
2019 ◽  
Vol 12 (4) ◽  
pp. 601 ◽  
Author(s):  
Tatyana Elkin ◽  
Stacy Copp ◽  
Ryan Hamblin ◽  
Jennifer Martinez ◽  
Gabriel Montaño ◽  
...  
Keyword(s):  
Polyethylene Glycol ◽  
Block Copolymers ◽  
Self Assembly ◽  
Chain Transfer ◽  
Raft Polymerization ◽  
Amphiphilic Block Copolymers ◽  
Transmission Electron ◽  
Reversible Addition ◽  
Efficient Route ◽  
High Yields

Polystyrene-b-polyethylene glycol (PS-b-PEG) amphiphilic block copolymers featuring a terminal tridentate N,N,N-ligand (terpyridine) were synthesized for the first time through an efficient route. In this approach, telechelic chain-end modified polystyrenes were produced via reversible addition-fragmentation chain-transfer (RAFT) polymerization by using terpyridine trithiocarbonate as the chain-transfer agent, after which the hydrophilic polyethylene glycol (PEG) block was incorporated into the hydrophobic polystyrene (PS) block in high yields via a thiol-ene process. Following metal-coordination with Mn2+, Fe2+, Ni2+, and Zn2+, the resulting metallo-polymers were self-assembled into spherical, vesicular nanostructures, as characterized by dynamic light scattering and transmission electron microscopy (TEM) imaging.

scholarly journals Thermoresponsive and Redox Behaviors of Poly(N-isopropylacrylamide)-Based Block Copolymers Having TEMPO Groups as Their Side Chains

2013 ◽  
Vol 2013 ◽  
pp. 1-9 ◽  
Author(s):  
Toru Uemukai ◽  
Tomoya Hioki ◽  
Manabu Ishifune
Keyword(s):  
Block Copolymers ◽  
Chain Transfer ◽  
Raft Polymerization ◽  
Solution Temperature ◽  
Thermoresponsive Polymer ◽  
Critical Solution Temperature ◽  
Redox Active ◽  
Reversible Addition ◽  
Polymerization Conditions ◽  
Active Block

Thermoresponsive and redox-active block copolymers having 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) moieties have been synthesized by using the reversible addition-fragmentation chain transfer (RAFT) polymerization technique.N-Isopropylacrylamide (NIPAAm) and 2,2,6,6-tetramethylpiperidyl methacrylate (TEMPMA) monomers were copolymerized stepwise under RAFT polymerization conditions to afford the thermoresponsive block copolymers, PNIPAAm-block-PTEMPMA and PNIPAAm-block-PTEMPMA-block-PNIPAAm. Oxidation of tetramethylpiperidine groups in the copolymers successfully afforded the corresponding TEMPO-containing block copolymers. The resulting triblock copolymer was found to be thermoresponsive showing lower critical solution temperature (LCST) at 34∘C in its aqueous solution. Redox behavior of the resulting copolymer was observed by cyclic voltammetry. The potential of anodic current peak changed below and above the LCST of the block copolymer. These results indicate that the phase transition of thermoresponsive polymer influences the redox potential of TEMPO moieties.

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.

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