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. 2025 Jun 24;11(7):488.
doi: 10.3390/gels11070488.

Radiation-Induced Synthesis of Polymer Networks Based on Thermoresponsive Ethylene Glycol Propylene Glycol Monomers

Andjelka Stolic  1 , Zorana Rogic Miladinovic  1 , Maja Krstic  1 , Georgi Stamboliev  1   2 , Vladimir Petrovic  3 , Edin Suljovrujic  1
Affiliations

Radiation-Induced Synthesis of Polymer Networks Based on Thermoresponsive Ethylene Glycol Propylene Glycol Monomers

Andjelka Stolic et al. Gels. .

Abstract

In this paper, different poly((ethylene glycol)-(propylene glycol)) methacrylate (P(EGPG)MA) hydrogels were synthesized by gamma-radiation-induced polymerization and crosslinking from a monomer-bisolvent mixture using the following monomers: (ethylene glycol)6 methacrylate (EG6MA), ((ethylene glycol)6-(propylene glycol)3) methacrylate (EG6PG3MA), ((propylene glycol)6-(ethylene glycol)3) methacrylate (PG6EG3MA), and (propylene glycol)5 methacrylate (PG5MA), along with different water/ethanol compositions as the solvent. The monomer-bisolvent mixture was exposed to various radiation doses (5, 10, 15, 25, and 50 kGy). Considerable emphasis was placed on optimizing and tuning the reaction conditions necessary for the fabrication of methacrylic networks with pendant EGPG terminals. A further investigation was conducted on the effects of monomer composition, different preparation conditions, and radiation processing on thermal properties, microstructure, swelling behavior, and volume phase transition. Special attention was dedicated to PPG6EG3MA hydrogel, whose volume phase transition temperature is near physiological temperatures. This study identifies an optimal radiation dose and a water/ethanol solvent ratio for the synthesis of the radiation-induced hydrogels. Employing ionizing radiation within the sterilization dose range enables the simultaneous fabrication and sterilization of these hydrogels, offering an efficient production process. The findings provide new insights into the role of bisolvent composition on hydrogel formation and properties, and they present practical guidelines for optimizing hydrogel synthesis across a wide range of applications.

Keywords: EGPG unit; hydrogel; radiation synthesis; thermoresponsive polymer; water/ethanol.

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Conflict of interest statement

Author Georgi Stamboliev was employed by the company Global Supply Line. The remaining authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest.

Figures

Figure 1
Figure 1
(a) UV-Vis transmittance profile for 10 wt% of EG6MA, EG6PG3MA, PG6EG3MA, and PG5MA monomers at 650 nm against different water/ethanol ratios recorded at room temperature. (b) Transmittance profile at 650 nm for 10 wt% of EG6MA, EG6PG3MA, PG6EG3MA, and PG5MA monomers in water against temperature. (c) Gel content for an absorbed dose of 25 kGy for PEG6MA, PEG6PG3MA, PPG6EG3MA, and PPG5MA hydrogels. (d) Transmittance profile at 650 nm for 10 wt% PG6EG3MA monomers in different water/ethanol ratios. The red horizontal dotted lines highlight the theoretically determined LCST values from the cloud point method.
Figure 2
Figure 2
(a) Gel content of PPG5MA, PPG6EG3MA, PEG6PG3MA, and PEG6MA hydrogels as a function of applied absorbed dose; (b) FTIR spectra of monomers/hydrogels/xerogels in the single bond region (3500–2500 cm−1) and double bond region (2000–1500 cm−1). The scans were shifted vertically for clarity.
Figure 3
Figure 3
(a) Digital photograph of hydrogels swollen to equilibrium in pH 7.4 buffer solution at three different temperatures: 5, 25, and 37 °C. (b) Equilibrium swelling degree (Qe) and DSC heating scan of PPG6EG3MA hydrogel in pH 7.4 buffer solution from 3 to 90 °C. (c) SEM images of PPG6EG3MA hydrogel swollen to equilibrium at three different temperatures (5, 25, and 37 °C) in pH 7.4 buffer solution before lyophilization.
See this image and copyright information in PMC

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