Preparation of ABC triblock copolymers of N-alkyl substituted acrylamides by RAFT polymerization

2007 ◽  
Vol 85 (6) ◽  
pp. 407-411 ◽  
Author(s):  
Ya Cao ◽  
X X Zhu

Reversible addition-fragmentation chain transfer (RAFT) polymerization of N-alkyl substituted acrylamides has been carried out by the use of a trithiocarbonate (2-dodecylsulfanylthiocarbonyl-sulfanyl-2-methyl propionic acid) as the RAFT reagent. The N-alkyl groups of the acrylamide monomers are important in the RAFT process. N-alkyl monosubstituted polyacrylamides are found to be active macro-chain transfer agents, while N,N-disubstituted monomers can react easily with them to form a sequent block. We have designed a synthetic pathway to successfully prepare ABC triblock copolymers of N-alkyl substituted acrylamides with low polydispersities (PDI < 1.20) by a three-step RAFT polymerization process.Key words: block copolymers, RAFT polymerization, N-alkyl substituted acrylamides, thermosensitive polymers.

2015 ◽  
Vol 6 (15) ◽  
pp. 2919-2933 ◽  
Author(s):  
Nagaraj Patil ◽  
Céline Falentin-Daudré ◽  
Christine Jérôme ◽  
Christophe Detrembleur

This paper describes the reversible addition–fragmentation chain transfer (RAFT) polymerization of mussel-inspired acetonide-protected dopamine (meth)acrylamide monomers (ADA and ADMA) and its implementation to the synthesis of innovative ambivalent block copolymers.


2013 ◽  
Vol 66 (12) ◽  
pp. 1564 ◽  
Author(s):  
Lily A. Dayter ◽  
Kate A. Murphy ◽  
Devon A. Shipp

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.


2019 ◽  
Vol 10 (19) ◽  
pp. 2424-2435 ◽  
Author(s):  
Bingjie Zhao ◽  
Sen Xu ◽  
Sixun Zheng

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.


Materials ◽  
2019 ◽  
Vol 12 (4) ◽  
pp. 601 ◽  
Author(s):  
Tatyana Elkin ◽  
Stacy Copp ◽  
Ryan Hamblin ◽  
Jennifer Martinez ◽  
Gabriel Montaño ◽  
...  

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.


2014 ◽  
Vol 934 ◽  
pp. 75-79 ◽  
Author(s):  
Xiao Feng Ye ◽  
Mi Zhou ◽  
Jing Ying Hu ◽  
Xin Qian

To develop a new drug delivery matrix with the suitable responsive interval, a well-defined triblock copolymer MPEG-b-PNIPAM-b-MPEG was synthesized by reversible addition fragmentation chain transfer (RAFT) polymerization. Then, the supramolecular hydrogels were fabricated via inclusion complexation with α-cyclodextrin (α-CD) and the triblock copolymers in aqueous solutions. The triblock copolymers were characterized by 1H NMR and gel permeation chromatography (GPC), and the supramolecular structures of hydrogels was confirmed by DSC. The resultant hydrogels was found to be thermo-sensitive, and the response interval could be modulated by controlling the content of PNIPAM.


2017 ◽  
Vol 13 ◽  
pp. 1310-1315 ◽  
Author(s):  
Jessica Hilschmann ◽  
Gerhard Wenz ◽  
Gergely Kali

The aqueous reversible addition fragmentation chain-transfer (RAFT) copolymerization of isoprene and bulky comonomers, an acrylate and an acrylamide in the presence of methylated β-cyclodextrin was employed for the first time to synthesize block-copolyrotaxanes. RAFT polymerizations started from a symmetrical bifunctional trithiocarbonate and gave rise to triblock-copolymers where the outer polyacrylate/polyacrylamide blocks act as stoppers for the cyclodextrin rings threaded onto the inner polyisoprene block. Statistical copolyrotaxanes were synthesized by RAFT polymerization as well. RAFT polymerization conditions allow control of the composition as well as the sequence of the constituents of the polymer backbone which further effects the CD content and the aqueous solubility of the polyrotaxane.


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