Polymer Chemistry Blog

Despax et al. report the synthesis of triblock copolymers and their application as thermoresponsive hydrogels.

Temperature responsive gelators can benefit a wide range of biomedical applications and typically comprised of triblock copolymers with a central hydrophilic block and terminal blocks that undergo a hydrophilic to hydrophobic transition at a specific temperature. However, typical ABA triblock copolymers obtained from commercially available monomers require concentrations of at least 50-100 g L^-1.

Harrisson, Destarac and co-workers have managed to circumvent this by synthesizing high molecular weight triblock copolymers via low temperature reversible addition-fragmentation chain-transfer (RAFT) gel polymerization. The targeted triblock copolymers were based on polydimethylacrylamide (PDMA) as the long central hydrophilic block and poly(N-isopropylacrylamide) (PNIPAM) as the shorter terminal blocks and the gel formation was initially demonstrated via vial-inversion tests.

Two different molecular weight triblock copolymers were tested with the PDMA block varying from 58 kg mol^-1 to 421 kg mol^-1 showing self-supporting gels at 30 g L^-1 and 6 g L^-1 concentration respectively, which is already a significant improvement over previously reported materials. As the vial-inversion test is subject to experimental variations, a more objective measure of the effect of the temperature was obtained from the evolution of the storage and loss moduli of aqueous polymer solutions.

For the lower molecular weight polymer, a two-step transition consisting of an initial thickening of the solution at the lower critical solution temperature (LCST) of PNIPAM occurred followed by gel formation at 38–39 °C requiring a minimum concentration of 20 g L^-1. For the longer polymer, only the second transition was observed; gel formation occurred at 40-45 °C with a minimum concentration of 4 g L^-1. With a storage modulus of only 0.1 Pa however, this gel is likely too soft for practical use.

In an attempt to improve the mechanical properties of the gels, 2-acrylamido-2-methylpropanesulfonic acid was also incorporated (20 mol% of DMA) resulting on the formation of self-supporting gels at 2 g L^-1, an order of magnitude improvement over previously-reported ABA copolymers. These results approach the performance obtained from exotic polymers such as polyisocyanopeptides.

Tips/comments directly from the authors:

1. High monomer concentrations are helpful to obtain high molecular weights. However, the polymerization of acrylamides is very exothermic so it is important not to exceed 30 wt%.
2. As very low initiator concentrations are used, it is important to thoroughly degas all solutions prior to polymerization.
3. Take care to exclude any air bubbles from the solution when carrying out rheology measurements.

Read this exciting research for free until 03/07/2016 through a registered RSC account:

Low concentration thermoresponsive hydrogels from readily accessible triblock copolymers
L. Despax, J. Fitremann, M. Destarac and S. Harrisson
Polym. Chem., 2016, 7, 3375-3377
DOI: 10.1039/C6PY00499G
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About the webwriter

Dr. Athina Anastasaki is a web writer for Polymer Chemistry. She is currently an Elings fellow working alongside Professor Craig Hawker at the University of California, Santa Barbara (UCSB).

Kristufek et al. report the synthesis of rapidly-cured isosorbide-based cross-linked polycarbonate elastomers.

Inexpensive starting materials from natural products (such as isosorbide, isomannide etc.) can allow for natural material to begin to compete with and (why not?) eventually replace petrochemicals as a source of monomers. Isosorbide-based materials in particular have attracted considerable attention due to both the rigidity of their fused ring systems and the easily-modifiable dual hydroxyl functionalities. However, the utility of isosorbide-based materials for elastomers is perhaps more limited. As such, in the current article, Wooley and co-workers aim to produce rapidly-photo-cross-linked isosorbide-based elastomers via thiol-ene chemistry that will have the additional potential to hydrolytically break down into their original building blocks.

This novel cross-linked network system was elegantly synthesized using a naturally-derived monomer, isosorbide dialloc (IDA) and cross linked with tri-methylpropane tris(3-mercaptopropionate) (TMPTMP) yielding IDA-co-TMPTMP, an optically transparent elastomer. All the IDA-co-TMPTMP networks were obtained by environmentally friendly methods including solvent-free conditions, low catalyst loading and UV irradiation. Importantly, a study of a constant UV cure time (1 minute) and variation of the thermal curing times led to the conclusion that this material is near its optimal thermal and mechanical properties without requiring post-cure heating.

The thermal decomposition temperature of the networks were consistent (320 °C) while the glass transition temperature remained below room temperature for all samples with a % elongation of 220-340%. The hydrolytic degradation of the material was also evaluated and found to afford 8.3±3.5% and 97.7±0.3% mass remaining after 60 days under accelerated basic and physiological neutral buffer conditions respectively. Finally, a cell viability assay and fluorescence imaging with adherent cells were also reported in order to show the potential of this material as a biomedical substrate. In conclusion, the rapid synthesis of this optically transparent flexible elastomer presented very interesting properties that could be very useful in biomedical applications or as environmentally-friendly materials.

Tips/comments directly from the authors:

1. Because DMPA dissolves slowly in the reaction mixture, it is important to keep it in the dark while mixing and allow it to fully dissolve, resulting in the most uniform materials.
2. Glass slides were used as the molds to maximize the light exposure to the reaction mixture of the two monomers, ensuring the rapid curing time.
3. During the degradation study, it is important to change the solution at short (ca. 2 days), constant intervals to provide consistent results.

Rapidly-cured isosorbide-based cross-linked polycarbonate elastomers by T.S. Kristufek, S.L. Kristufek, L.A. Link, A.C. Weems, S. Khan, S.M. Lim, A.T. Lonnecker, J.E. Raymond, D.J. Maitland and K.L. Wooley, Polym. Chem., 2016, 7, 2045-2056, DOI: 10.1039/C5PY01659B