Conetworks and Organogels of Poly(methyl acrylate) Crosslinked with Degradable, Disulfide and β-Thioester Containing Bisacrylate Macromonomer.
- 1Polymer Chemistry and Physics Research Group, Institute of Materials and Environmental Chemistry, Research Centre for Natural Sciences, Magyar tudósok körútja 2, H-1117 Budapest, Hungary.
- 2George Hevesy PhD School of Chemistry, Institute of Chemistry, Faculty of Science, Eötvös Loránd University, Pázmány Péter sétány 1/A, H-1117 Budapest, Hungary.
- 3Functional Nanoparticles Research Group, Institute of Materials and Environmental Chemistry, Research Centre for Natural Sciences, Magyar tudósok körútja 2, H-1117 Budapest, Hungary.
Abstract
Here, we report, for the first time, on a new class of sulfur-containing double hydrophopbic conetworks, poly(methyl acrylate)-l-poly(3,6-dioxa-1,8-octane-dithiol-co-poly(ethylene glycol) diacrylate) (PMA-l-P(DODT-co-PEGDA). Direct one-pot synthesis of acrylate-telechelic P(DODT-co-PEGDA) macromonomer in a gram-scale for the preparation of the conetworks was obtained by copolymerization of DODT with PEGDA via simultaneous oxidative disulfide formation and thiol-ene Michael addition click reactions. Conetworks with a broad composition range of 20-70 wt% sulfur-rich P(DODT-co-PEGDA) macrocrosslinker contents were obtained by radical copolymerization. High gel fractions and composition near to that of the feed ratios verified successful conetwork synthesis. DSC analysis indicates forced blending of the immiscible PMA and P(DODT-co-PEGDA) in the conetworks by one single Tg, which deviates from both the additive rule and the Fox equation for miscible blends. These novel conetworks exhibit high thermal stability up to ~300 °C and independent decomposition patterns of the components in two separate steps. The PMA-l-P(DODT-co-PEGDA) conetworks behave as organogels by swelling in organic solvents, such as THF, acetone, toluene, with composition dependent swelling degrees up to ~900%. Degradation by breaking the disulfide bonds with thiols followed by hydrolysis with NaOH led to complete disintegration of the PMA-l-P(DODT-co-PEGDA) conetworks. These findings enable establishing a new platform for the rational design of a variety of novel sulfur-containing functional and degradable macromolecular assemblies.
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BibTeX
@article{aitkazina2026conetworks,
title = {{Conetworks and Organogels of Poly(methyl acrylate) Crosslinked with Degradable, Disulfide and β-Thioester Containing Bisacrylate Macromonomer.}},
author = {Aiman Aitkazina and Ákos Szabó and László Trif and Klára Verebélyi and Dóra Fecske and Anna Petróczy and Béla Iván},
journal = {Gels (Basel, Switzerland)},
year = {2026},
month = sep,
doi = {10.3390/gels12100862},
url = {https://europepmc.org/article/MED/42929897},
note = {CC BY},
}
RIS
TY - JOUR
TI - Conetworks and Organogels of Poly(methyl acrylate) Crosslinked with Degradable, Disulfide and β-Thioester Containing Bisacrylate Macromonomer.
AU - Aiman Aitkazina
AU - Ákos Szabó
AU - László Trif
AU - Klára Verebélyi
AU - Dóra Fecske
AU - Anna Petróczy
AU - Béla Iván
PY - 2026
DA - 2026/09/24
JO - Gels (Basel, Switzerland)
DO - 10.3390/gels12100862
UR - https://europepmc.org/article/MED/42929897
AB - Here, we report, for the first time, on a new class of sulfur-containing double hydrophopbic conetworks, poly(methyl acrylate)-l-poly(3,6-dioxa-1,8-octane-dithiol-co-poly(ethylene glycol) diacrylate) (PMA-l-P(DODT-co-PEGDA). Direct one-pot synthesis of acrylate-telechelic P(DODT-co-PEGDA) macromonomer in a gram-scale for the preparation of the conetworks was obtained by copolymerization of DODT with PEGDA via simultaneous oxidative disulfide formation and thiol-ene Michael addition click reactions. Conetworks with a broad composition range of 20-70 wt% sulfur-rich P(DODT-co-PEGDA) macrocrosslinker contents were obtained by radical copolymerization. High gel fractions and composition near to that of the feed ratios verified successful conetwork synthesis. DSC analysis indicates forced blending of the immiscible PMA and P(DODT-co-PEGDA) in the conetworks by one single Tg, which deviates from both the additive rule and the Fox equation for miscible blends. These novel conetworks exhibit high thermal stability up to ~300 °C and independent decomposition patterns of the components in two separate steps. The PMA-l-P(DODT-co-PEGDA) conetworks behave as organogels by swelling in organic solvents, such as THF, acetone, toluene, with composition dependent swelling degrees up to ~900%. Degradation by breaking the disulfide bonds with thiols followed by hydrolysis with NaOH led to complete disintegration of the PMA-l-P(DODT-co-PEGDA) conetworks. These findings enable establishing a new platform for the rational design of a variety of novel sulfur-containing functional and degradable macromolecular assemblies.
SN - 2310-2861
ER -