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PAAm/CMC/nanoclay nanocomposite hydrogel: understanding the influence of initiators on the chain-growth mechanisms

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Abstract

In this study, heat measurements were used to investigate the influence of three initiators on the chain-growth mechanisms of polyacrylamide/carboxymethylcellulose/nanoclay nanocomposite hydrogels. All the matrices had highly interconnected porous surfaces with intercalated configurations. Swelling degree measurements were conducted to investigate the effect of the various formed chains on the physicochemical properties of these matrices. According to the findings, hydrogels synthesized using a potassium persulfate initiator had the highest water absorbency (around 40.8 ± 0.8 g.g^−1), followed by those synthesized using sodium persulfate (38.1 ± 1.0 g.g^−1) and ammonium persulfate initiators (34.8 ± 0.7 g.g^−1). The nanoclay-containing nanocomposite had a similar water absorption tendency. Additionally, all the nanocomposites had a lower swelling degree than pure hydrogel because nanoclay acted as a physical crosslinker in the polymeric matrix, decreasing the chain elasticity and water sorption ability. Different physicochemical properties were then generated due to the difference in polymerization mechanisms. Chain combination was the preferred termination mechanism for the polymerization of the hydrogel with the highest water absorbency. It was also plausible to assume that chain transfer reactions favored the termination mechanisms of the polymerization of the nanocomposites synthesized using NaPS and APS initiators, generating polymeric chains with low molecular weight and reducing the water absorption capacity. The insertion of nanoclay inhibited the start of the polymerization initiation step by preventing the initiator from attacking the monomer. Thus, a better understanding of the interaction between the initiators and hydrogel components can aid in the synthesis of hybrid nanocomposites with desirable characteristics and properties.

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Acknowledgements

The authors would like to thank UNESP, grants 2018/18697-1; 2013/03643-0; 2013/07296-2 São Paulo Research Foundation (FAPESP), and CNPq (MRM 312530/2018-8; FAA 405680/2016-3; 312414/2018-8; 316174/2021-1). This paper was possible thanks to the scholarship granted from the Brazilian Federal Agency for Support and Evaluation of Graduate Education (CAPES), in the scope of the Program CAPES-PrInt, process number 88887.310463/2018-00, International Cooperation Project number 88887.310309/2018-00. This study was financed in part by CAPES–“Finance Code 001.”

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R.S.F, F.C.T, C.R.F.J, U.G.Y conceived, colletected, and analysed the data. M.R.M supervised, and F.A.A conceptualized and supervised the manuscript. All authors wrote and contributed to manuscript revision, read, and approved the submitted version.

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Correspondence to Fauze Ahmad Aouada.

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da Silva Fernandes, R., Tanaka, F.C., Junior, C.R.F. et al. PAAm/CMC/nanoclay nanocomposite hydrogel: understanding the influence of initiators on the chain-growth mechanisms. J Polym Res 29, 519 (2022). https://doi.org/10.1007/s10965-022-03373-z

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