title: Polyisobutylene-Based pH-Responsive Self-Healing Polymeric Gels.
abstract: This work demonstrates the successful application of dynamic covalent chemistry for the construction of self-healing gels from side-chain primary amine leucine pendant diblock copolymers of polyisobutylene (PIB) ((P(H2N-Leu-HEMA)-b-PIB)) in the presence of PIB based dialdehyde functionalized cross-linker (HOC-PIB-CHO) through imine (-HC═N-) bond formation without aiding any external stimuli. Gels were synthesized in 1,4-dioxane at room temperature at varied wt % of gelator concentration, [H2N]/[CHO] ratios and molecular weight of the block segments. The mechanical property of gels was examined by rheological measurements. We observed higher value of storage modulus (G') than the loss modulus (G″) within the linearity limits of deformation, indicating the rheological behavior in the gel is dominated by an elastic property rather than a viscous property. The G' values significantly depend upon the extent of cross-linking in the gel network. To establish self-healing property of the gels, rheology analysis through step-strain measurements (strain = 0.1 to 200%) at 25 °C was performed. The polymeric gel network shows reversible sol-gel transition for several cycles by adjusting the pH of the medium with the help of hydrochloric acid (HCl) and triethylamine (Et3N) triggers. FT-IR spectroscopy established formation of imine bonds in the gel network and these gels showed poor swelling behavior in various organic solvents because of the small interstitial porosity, confirmed by field emission-scanning electron microscopy (FE-SEM).
authors.affiliation: †Polymer Research Centre, Department of Chemical Sciences, Indian Institute of Science Education and Research Kolkata, Mohanpur-741246, Nadia, West Bengal India.
authors.forename: Ujjal
authors.initials: U
authors.lastname: Haldar
authors.affiliation: †Polymer Research Centre, Department of Chemical Sciences, Indian Institute of Science Education and Research Kolkata, Mohanpur-741246, Nadia, West Bengal India.
authors.forename: Kamal
authors.initials: K
authors.lastname: Bauri
authors.affiliation: ‡Polymer Science Program, Department of Chemistry, University of Massachusetts Lowell, One University Avenue, Lowell, Massachusetts 01854, United States.
authors.forename: Ren
authors.initials: R
authors.lastname: Li
authors.affiliation: ‡Polymer Science Program, Department of Chemistry, University of Massachusetts Lowell, One University Avenue, Lowell, Massachusetts 01854, United States.
authors.forename: Rudolf
authors.initials: R
authors.lastname: Faust
authors.affiliation: †Polymer Research Centre, Department of Chemical Sciences, Indian Institute of Science Education and Research Kolkata, Mohanpur-741246, Nadia, West Bengal India.
authors.forename: Priyadarsi
authors.initials: P
authors.lastname: De
keywords: amino acids; polyisobutylene; reversible sol−gel transition; self-healing; storage modulus