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A new approach for synthesis of cyclic poly(N-isopropylacrylamide), for applying in biomaterial applications

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Abstract

This research reports the successful synthesis of the cyclic poly(N-isopropyl acrylamide) (cPNIPAAM) by a new method. For this purpose, \(\alpha\), ω-difunctionalized precursor was synthesized, applying a free radical polymerization process in the methanol solvent, and using the nitroxide component, hydroxy-TEMPO, as the terminator for the first time. Then, end-to-end equilibrium, with an appropriate coupling agent, was utilized for cyclization reaction in the two solvents of water and dimethylformamide (DMF). Using a terminator to produce functionalized chains led to controlled molecular weight polymers. As a result, reduced molecular weight precursors were created, resulting in smaller rings with improved water solubility, LCST temperature and more environmentally compatible friendly products, particularly in medicinal objectives. In comparison with previous techniques, these characteristics represent the precise innovation of our study. The yield and optimum polymerization conditions were provided. The polymer products were characterized by FTIR, 1HNMR, GPS, TLC, DSC, DLS and viscometry methods. The morphology and molecular weight were compared with the previously produced polymers. The results confirmed the formation of polymers with lower molecular weight compared to previous methods. Despite its lower cyclization yield, water was a better solvent compared to DMF.

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Data availability

The datasets used and/or analyzed during the current study available from the corresponding author on reasonable request.

Abbreviations

ATRP:

Atom transfer radical polymerization

cPNIPAAM:

Cyclic poly(N-isopropylacrylamide)

DLS:

Dynamic light scattering

DMF:

Dimethylformamide

DSC:

Differential scanning calorimetry

DMSO:

Dimethyl sulfoxide

FTIR:

Fourier transform infrared spectroscopy

GPC:

Gel permeation chromatography

HNMR:

Hydrogen nuclear magnetic resonance

LCST:

Lower critical solution temperature

M n :

The number average molecular weight

M v :

Viscosity average molecular weight

M w :

Weight average molecular weight

NIPAAM:

N-Isopropylacrylamide

NMP:

Nitroxide-mediated polymerization

PNIPAAM:

Poly(N-isopropylacrylamide)

RAFT:

Addition-fragmentation chain transfer

T g :

Glass transition temperature

T m :

Melting point

TLC:

Thin layer chromatography

THF:

Tetrahydrofuran

W i :

Weight of initiator

W m :

Weight of monomer

W p :

Weigh of linear polymer

W pi :

Weight of 2-chloro-1-methylpyridinium iodide

W t :

Weight of terminator

W tea :

Weight of triethylamine

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Acknowledgements

The authors would like to take this opportunity to appreciate the Research Deputy to the University of Kashan for financially supporting this research under the Grant code of Pajoohaneh-1400/18.

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Authors and Affiliations

  1. Department of Chemical Engineering, Faculty of Engineering, University of Kashan, Kashan, 87317-53153, Iran

    Sahar Daneshyan & Gholamhossein Sodeifian

  2. Laboratory of Supercritical Fluids and Nanotechnology, University of Kashan, Kashan, 87317-53153, Iran

    Sahar Daneshyan & Gholamhossein Sodeifian

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  1. Sahar Daneshyan
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Correspondence to Gholamhossein Sodeifian.

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Daneshyan, S., Sodeifian, G. A new approach for synthesis of cyclic poly(N-isopropylacrylamide), for applying in biomaterial applications. Polym. Bull. 81, 929–949 (2024). https://doi.org/10.1007/s00289-023-04741-5

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  • DOI: https://doi.org/10.1007/s00289-023-04741-5

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