Effect of copolymer composition of RAFT/MADIX-derived N-vinylcaprolactam/N-vinylpyrrolidone statistical copolymers on their thermoresponsive behavior and hydrogel properties

Zhao, Xuange; Coutelier, Olivier; Nguyen, Hanh H.; Delmas, Céline; Destarac, Mathias; Marty, Jean‐Daniel

doi:10.1039/c5py00606f

Cited by 31 publications

(57 citation statements)

References 48 publications

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“…RAFT polymerization in bulk, were reported in 2008. 21 Following that publication, NVCL has been RAFT/MADIX polymerized by several groups, in bulk, 22,23 in various different organic solvents, [24][25][26][27][28][29][30] and also in water/ ethanol mixtures. 31 NVCL has also been synthesized via ATRP 32,33 and cobalt-mediated polymerization.…”

Section: Introductionmentioning

confidence: 99%

The emulsion polymerization induced self-assembly of a thermoresponsive polymer poly(N-vinylcaprolactam)

2019

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Section: Introductionmentioning

confidence: 99%

The emulsion polymerization induced self-assembly of a thermoresponsive polymer poly(N-vinylcaprolactam)

2019

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“…35, 37, 39 or MNHS 34 or increase the PNVCL concentration in the turbidimetry assays. Herein, the solution behavior of the pure homopolymers presented in Table 1 was also studied in order to create a library of polymers with different LCSTs.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of well-defined alkyne terminated poly(N-vinyl caprolactam) with stringent control over the LCST by RAFT

et al. 2016

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The reversible addition-fragmentation chain transfer (RAFT) of N-vinyl caprolactam (NVCL) using two new xanthates with alkyne functionalities is reported. The kinetic data obtained for polymerization of this non-activated monomer using a protected alkyne-terminated RAFT agent (PAT-X1) revealed a linear increase of the polymer molecular weight with the monomer conversion as well as low dispersity (Đ) during the entire course of the polymerization. The system reported here allowed us to enhance the final conversion, diminish Đ and reduce the polymerization temperature compared to the typical values reported in the scarce literature available for the RAFT polymerization of NVCL. The resulting PNVCL was fully characterized using 1H nuclear magnetic resonance (1H NMR), matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF-MS), Fourier-transform infrared spectroscopy (FTIR) and gel permeation chromatography (GPC) techniques. The temperature-responsive features of PNVCL in aqueous solutions were fully investigated under different conditions using turbidimetry. The presented strategy allows the synthesis of well-defined PNVCL with sharp and reversible phase transition temperatures around 37 °C. By manipulating the polymer molecular weight, or the solution properties, it is possible to tune the PNVCL phase transition. As a proof-of concept, the alkyne functionalized PNVCL was used to afford new linear block copolymers, by reacting with an azide-terminated poly(ethylene glycol) (N3-PEG) through the copper catalyzed azide-alkyne [3+2] dipolar cycloaddition (CuAAC) reaction. The results presented establish a robust system to afford the synthesis of PNCVL with fine tuned characteristics that will enable more efficient exploration of the remarkable potential of this polymer in biomedical applications.

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“…Dai et al also report a similar system of a pH‐induced reversible micellization . Marty et al recently studied the effect of copolymer composition of RAFT/MADIX‐derived poly( N ‐vinylcaprolactam‐ co ‐ N ‐vinylpyrrolidone) statistical copolymers on their thermoresponsive behavior and hydrogel properties . In most of these studies of dual dual‐responsive polymers, either AB‐type di‐block copolymers or ABC‐type tri‐block copolymers have been used.…”

Section: Introductionmentioning

confidence: 99%

Dual Stimuli‐Responsive Self‐Assembly Behavior of a Tailor‐Made ABC‐Type Amphiphilic Tri‐Block Copolymer

Pal

Kather

Banerjee

et al. 2020

Journal of Polymer Science

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This investigation describes the synthesis of a dual stimuli‐responsive, amphiphilic ABC tri‐block copolymer (BCP) based on the functional monomers via RAFT polymerization. In this case, ABC‐type BCP was prepared based on N‐isopropylacrylamide, n‐butyl acrylate, and 4‐vinylpyridine in DMF solvent using cyanomethyl dodecyl trithiocarbonate as the RAFT agent and azobisisobutyronitrile as a thermal initiator in a subsequent macro‐RAFT approach, respectively. The BCPs were characterized by SEC, 1H‐NMR, FTIR spectroscopy, and DSC analyses. Temperature and pH‐dependent properties of the smart BCP micelles in aqueous medium were investigated using dynamic light scattering. Transmission electron microscopic images were taken at cryogenic and dry conditions to study the morphology of molecular assemblies of block copolymers in an aqueous medium. The phase and topographical images were captured by atomic force microscopy to understand the assembly of block copolymers in solvents of different polarities. The morphology of BCP micelles was transformed from flower‐like to spherical in the presence of solvents with different polarities (H2O or CHCl3).

show abstract

Effect of copolymer composition of RAFT/MADIX-derived N-vinylcaprolactam/N-vinylpyrrolidone statistical copolymers on their thermoresponsive behavior and hydrogel properties

Cited by 31 publications

References 48 publications

The emulsion polymerization induced self-assembly of a thermoresponsive polymer poly(N-vinylcaprolactam)

The emulsion polymerization induced self-assembly of a thermoresponsive polymer poly(N-vinylcaprolactam)

Synthesis of well-defined alkyne terminated poly(N-vinyl caprolactam) with stringent control over the LCST by RAFT

Dual Stimuli‐Responsive Self‐Assembly Behavior of a Tailor‐Made ABC‐Type Amphiphilic Tri‐Block Copolymer

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