Abstract

Poly(sodium 2-acrylamido-2-methylpropanesulfonate) (PAMPSNa) was prepared via reversible addition-fragmentation chain transfer (RAFT) radical polymerization. An ionic liquid polymer (PAMPSP4448) was then prepared by exchanging the pendant counter cation from sodium (Na+) to tributyl-n-octylphosphonium (P4448+). We studied the ultrasound- and thermo-responsive behaviors of PAMPSP4448 in water. When the aqueous PAMPSP4448 solution was heated from 5 to 50 °C, the solution was always transparent with 100% transmittance. Unimers and interpolymer aggregates coexisted in water in the temperature range 5–50 °C. Generally, hydrogen bonding interactions are broken as the temperature increases due to increased molecular motion. Above 25 °C, the size of the interpolymer aggregates decreased, because hydrophobic interactions inside them were strengthened by dehydration accompanying cleavage of hydrogen bonds between water molecules and the pendant amide or sulfonate groups in PAMPSP4448. Above 25 °C, sonication of the aqueous solution induced an increase in the collision frequency of the aggregates. This promoted hydrophobic interactions between the aggregates to form larger aggregates, and the aqueous solution became turbid. When the temperature was decreased below 8 °C, hydrogen bonds reformed between water molecules and the pendant amide or sulfonate groups, allowing PAMPSP4448 to redissolve in water to form a transparent solution. The solution could be repeatedly controlled between turbidity and transparency by sonication and cooling, respectively.

Highlights

  • The chemical and physical properties of stimuli-responsive polymers can be controlled by external stimuli such as temperature, pH, and light

  • Kohno et al [8,9] reported that lower critical solution temperature (LCST) behavior was observed at 57 ◦ C for aqueous poly(tetrabutylphosphonium styrenesulfonate) (PSSP4444 ), which was prepared by exchanging the counter cation, sodium (Na+ ) in poly(sodium styrenesulfonate) (PSSNa), with tetrabutylphosphonium (P4444 + )

  • PAMPSP4448, was synthesized by exchanging the pendant counter cation from Na+ to P4448 + in PAMPSNa prepared via reversible addition-fragmentation chain transfer (RAFT) radical polymerization (Figure S1)

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Summary

Introduction

The chemical and physical properties of stimuli-responsive polymers can be controlled by external stimuli such as temperature, pH, and light. Thermo-responsive polymers have been widely used as stimuli-responsive polymers Their lower critical solution temperature (LCST) behavior in water is well known [6,7]. Phosphonium hexylsulfonate), which was prepared by exchanging the counter chloride anion in poly(tributyl-4-vinylbenzyl phosphonium hexylsulfonate), which was prepared by exchanging the poly(tributyl-4-vinylbenzyl phosphonium chloride) to the hexylsulfonate anion, shows LCST-type counter chloride anion in poly(tributyl-4-vinylbenzyl phosphonium chloride) to the hexylsulfonate thermo-responsive behavior at 53 ◦ C in water [11]. Could be repeatedly controlled between turbidity and transparency via sonication and cooling, We studied the ultrasound- and thermo-responsive behavior of the aqueous PAMPSP4448 solution using respectively. We studied the ultrasound- and thermo-responsive behavior of the aqueous percent transmittance (%T), light scattering, transmission electron microscopy (TEM), and fluorescence.

Materials
Measurements
Synthesis of Polymers
Turbidimetry
Light Scattering
Fluorescence Probe
The Proposed Mechanism of Ultrasound- and Thermo-Responsive Behavior
When the solution
Conclusions
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