Thermoresponsive Polymer Gel Research Articles

Synthesis of thermo-responsive polymer gels composed of star-shaped block copolymers by copper-catalyzed living radical polymerization and click reaction

ABSTRACT In recent times, there has been a significant surge in research interest surrounding thermo-responsive water-soluble polyacrylamides, primarily due to their intriguing capability to undergo significant solubility changes in water. These polymers exhibit the remarkable ability to shift from a soluble to an insoluble state in response to temperature variations. The capacity of these polymers to dynamically respond to temperature changes opens up exciting avenues for designing smart materials with tunable properties, amplifying their utility across a spectrum of scientific and technological applications. Researchers have been particularly captivated by the potential applications of thermo-responsive water-soluble polyacrylamides in diverse fields such as drug delivery, gene carriers, tissue engineering, sensors, catalysis, and chromatography separation. This study reports the construction and functionalization of polymer gels consisting of a polymer network of polyacrylamide derivatives with nano-sized structural units. Specifically, thermo-responsive polymer gels were synthesized by combining well-defined star-shaped polymers composed of polyacrylamide derivatives with a multifunctional initiator and linking method through a self-accelerating click reaction. The polymerization system employed a highly living approach, resulting in polymer chains characterized by narrow molecular weight distributions. The method’s high functionality facilitated the synthesis of a temperature-responsive block copolymer gel composed of N-isopropyl acrylamide (NIPA) and N-ethyl acrylamide (NEAA). The resulting polymer gel, comprising star-shaped block copolymers of NIPA and NEAA, showcases smooth volume changes with temperature jumps.

Review of the Perspectives and Study of Thermo-Responsive Polymer Gels and Applications in Oil-Based Drilling Fluids.

Thermoresponsive polymer gels are a type of intelligent material that can react to changes in temperature. These materials possess excellent innovative properties and find use in various fields. This paper systematically analyzes the methods for testing and regulating phase transition temperatures of thermo-responsive polymer gels based on their response mechanism. The report thoroughly introduces the latest research on thermo-responsive polymer gels in oil and gas extraction, discussing their advantages and challenges across various environments. Additionally, it elucidates how the application limitations of high-temperature and high-salt conditions can be resolved through process optimization and material innovation, ultimately broadening the scope of application of thermo-responsive polymer gels in oil and gas extraction. The article discusses the technological development and potential applications of thermo-responsive polymer gels in oil-based drilling fluids. This analysis aims to offer researchers in the oil and gas industry detailed insights into future possibilities for thermo-responsive polymer gels and to provide helpful guidance for their practical use in oil-based drilling fluids.

Synthesis of thermoresponsive polymer gels with crosslinked domains containing iridium complexes for ammonia sensing and N-alkylation catalysis

Synthesis of thermoresponsive polymer gels with crosslinked domains containing iridium complexes for ammonia sensing and N-alkylation catalysis

Interactions in dopamine and indole loaded thermosensitive hydrogels seen by high sensitivity microDSC. Implications for drug delivery

Controlled and targeted drug delivery systems consist of a carrier matrix and one or more active ingredients. One of the roles of the matrix is to regulate the release of the drug. Uptake, release, differential scanning microcalorimetry (DSC) and powder X-ray diffraction (XRD) techniques were used to reveal the interactions governing the release of dopamine and indole from a thermoresponsive model polymer gel. The dopamine can be completely recovered from the loaded polymer matrix. The self-assembling affinity of the dopamine molecules reduces their interaction with the polymer, and the water molecules can form a uniform protecting water sheath. Thus neither the kinetics nor the temperature of the phase transition of the carrier matrix are influenced by the dopamine. The DSC results imply the formation of polymer and dopamine-rich domains above the phase transition. Indole, on the other hand, readily substitutes for the water molecules through the interaction between the C=O sites of the polymer and the NH groups of the drug. The loss of the protecting hydrophobic water and the decelerated fluctuation of the indole decorated polymer chains result in a much slower phase transition and a depleted phase transition temperature. The interaction between the carrier matrix and the indole results in a uniform distribution of the drug and after drying the indole is found in amorphous form. Dopamine, on the contrary, forms crystalline regions.

Supramolecular hydrogelation via host-guest anion recognition: Lamellar hydrogel materials for the release of cationic cargo

Supramolecular hydrogelation via host-guest anion recognition: Lamellar hydrogel materials for the release of cationic cargo

Preparation and characterization of thermoresponsive poly(N‐isopropylacrylamide‐co‐N‐isopropylmethacrylamide) hydrogel materials for smart windows

AbstractIn this study, a series of thermoresponsive cross‐linked copolymer poly [N‐isopropylacrylamide(NIPAm)‐co‐N‐isopropylmethacrylamide(NIPMAm)] (P‐M series samples: P‐M‐0, 10, 20, 30, 40, where numbers are co‐monomer contents) hydrogels were prepared by free radical polymerization using the main monomer N‐isopropylacrylamide (NIPAm), co‐monomer N‐isopropylmethacrylamide (NIPMAm), cross‐linking agent N, N‐methylenebisacrylamide, initiator (ammonium persulfate)/catalyst, and solvent water. In addition, a series of samples [P‐G series samples: P‐G‐0, 10, 20, 30, 40, where numbers are co‐solvent glycerol content) were prepared using P‐M‐40 as components and water/co‐solvent glycerol as a mixed solvent. The effects of co‐monomer NIPMAm and co‐solvent glycerol contents on the lower critical solution temperature (LCST)/freezing temperature and light transmittance as function of temperature of the prepared copolymer gels were investigated. The resulting thermoresponsive polymer gels had LCSTs in the range of 17.9 to 38.7°C and freezing points in the range of 6.3 to −38.5°C. These gels are suitable materials for smart windows that are responsive to various environmental conditions.

Synthesis, Phase-Transition Behaviour, and Oil Adsorption Performance of Porous Poly(oligo(ethylene glycol) Alkyl Ether Acrylate) Gels.

To probe the effects of pendant side-chain structures on the properties of porous thermoresponsive polymer gels, oligo(ethylene glycol) alkyl ether acrylates were polymerised in an aqueous medium under radical-mediated phase-separation conditions. The monomer structures varied according to the lengths and termini of their ethylene glycol side chains. The porous poly(oligo(ethylene glycol) alkyl ether acrylate) (POEGA) gels exhibited variable lower critical solution temperatures (LCSTs) but similar and rapid swelling–deswelling behaviours. Although the LCST of the poly(tri(ethylene glycol) monomethyl ether acrylate) (PTEGA) gel decreased with increasing aqueous NaCl or CaCl2 concentration, PTEGA showed excellent thermosensitivity in highly concentrated salt solutions, recommending its application in saline environments. Examination of PTEGA adsorption performance in an oil–water emulsion showed that n-tridecane adsorption increased with temperature. Although n-tridecane was effectively adsorbed at 70 °C, its release from the fully adsorbed PTEGA gel was difficult despite a temperature reduction from 70 to 20 °C.

Binding Energetics of Charged Amphiphilic Ligands to Thermoresponsive Biodegradable Poly(methoxyethylaminophosphazene) Hydrogels.

Changes in the affinity of the swollen and collapsed forms of a thermoresponsive polymer gel for targeted ligands can be directly estimated using a thermodynamic approach based on high-sensitivity differential scanning calorimetry (HS-DSC). For macromolecular ligands (proteins) bound to the gel, this method provides information on changes in their conformational stability, which is of crucial importance for the biological or pharmaceutical activity of the protein. We used HS-DSC for the study of interactions of two widely administrated drugs-gemfibrozil and ibuprofen-and two globular proteins-α-lactalbumin and BSA-with hydrogels of the cross-linked poly(methoxyethylaminophosphazene). The gel collapse resulted in a substantial increase in the gel affinity for the drugs. We obtained quantitative estimations of the affinity of the collapsed gels depending on the gel structure, pH, concentration of NaCl, and phosphate buffer (an inductor of the thermoresponsivity). The gels retained a high affinity for the drugs in the near-physiological conditions (ionic composition and pH). The binding curves of globular proteins to the gels in the swollen and collapsed states were obtained. The different proteins demonstrated the preferential binding to the swollen or collapsed state of the gels, presumably depending on the protein surface hydrophobicity. The proteins bound to the gel subchains retain their native tertiary structure and, therefore, maintain their functionality when immobilized in the polyphosphazene hydrogels.

Extreme thermodynamics with polymer gel tori: Harnessing thermodynamic instabilities to induce large-scale deformations.

When a swollen, thermoresponsive polymer gel is heated in a solvent bath, it expels solvent and deswells. When this heating is slow, deswelling proceeds homogeneously, as observed in a toroid-shaped gel that changes volume while maintaining its toroidal shape. By contrast, if the gel is heated quickly, an impermeable layer of collapsed polymer forms and traps solvent within the gel, arresting the volume change. The ensuing evolution of the gel then happens at fixed volume, leading to phase separation and the development of inhomogeneous stress that deforms the toroidal shape. We observe that this stress can cause the torus to buckle out of the plane, via a mechanism analogous to the bending of bimetallic strips upon heating. Our results demonstrate that thermodynamic instabilities, i.e., phase transitions, can be used to actuate mechanical deformation in an extreme thermodynamics of materials.

Coil-globule transitions drive discontinuous volume conserving deformation in locally restrained gels

The equilibrium volume of a thermoresponsive polymer gel changes dramatically across a temperature due to the coil–globule transitions of the polymers. When cofacially oriented nanosheets are embedded in such a gel, the composite gel deforms at the temperature, without changing the volume, and the response time is considerably shorter. We here theoretically predict that the deformation of the composite gel results from the fact that the nanosheets restrain the deformation of some polymers, while other polymers deform relatively freely. The unrestrained polymers collapse due to the coil–globule transitions and this generates the solvent flows to the restrained regions. The response time of this process is rather fast because solvent molecules travel only by the distance of the size of a nanosheet, instead of permeating out to the external solution. This concept may provide insight in the physics of composite gels and the design of thermoresponsive gels of fast response.

A thermoresponsive supramolecular polymer gel from a heteroditopic calix[4]pyrrole.

Supramolecular polymerization of calix[4]pyrroles bearing tethered carboxylate functional groups was reported in the form of their tetrabutylammonium salts. At high concentrations one of the calix[4]pyrroles with a shorter linker between the calixpyrrole core and the carboxylate unit was found to give a thermoresponsive supramolecular polymer gel.

Size distribution and elastic properties of thermo-responsive polymer gel microparticles in suspension probed by ultrasonic spectroscopy

The size distribution and the elasticity of thermo-responsive gel particles dispersed in water were examined in-situ by ultrasonic spectroscopy (US). Poly(N-isopropylacrylamide) (PNIPAM) gel particles, undergoing volume phase transition at 34°C were synthesized by redox polymerization in emulsion, and the temperature dependence of the acoustic properties was examined. The longitudinal velocity and the attenuation coefficient of particle exhibited a drastic change at the transition temperature, indicating the increase in the mechanical properties, such the longitudinal, bulk and shear moduli, due to the shrinkage of particles upon temperature stimulation. The shear modulus of monodisperse particles, and also the stiffness of the gel particles were evaluated.

Dipicolylamine Functionalized Polyfluorene Based Gel with Lower Critical Solution Temperature: Preparation, Characterization, and Application

A thermoresponsive fluorescent polymer gel with lower critical solution temperature (LCST) phase transition has been prepared by cooperating conjugated fluorene homopolymer poly(2,7-(9,9-di(8-di(2-picolyl)aminooctyl))fluorene) (PPAOF) and small organic dye sulforhodamine B (SRB) or its sodium salt (SRB-Na). The sol-gel phase transition originates from the electrostatic interactions between the protonated pyridyl/amino groups in PPAOF and the sulfonic groups in the organic dye molecules, as revealed by FTIR, variable-temperature 1H NMR spectroscopies, and cyclic voltammetry measurements. Consequently, the LCST value can be finely controlled by simply tuning the component concentrations. Moreover, due to the inefficient energy transfer, the resulting fluorescent polymer gel exhibits two independent emission bands at 440 and 577 nm, assigned to the characteristic emissions from fluorene homopolymer and organic dye, respectively. Furthermore, this fluorescent polymer gel exhibits a reversible electrofluorochromic (EFC) property with high fluorescence contrast when it is assembled in a single-layer supporting electrolyte-free EFC device. Most interestingly, different fluorescence colors can be achieved from the two electrodes of the device. Our findings may present a new way to design conjugated polymer based LCST gels and EFC materials.

Tuning Hydrogel Mechanics Using the Hofmeister Effect

The mechanical properties of hydrogels are commonly modified by changing the concentration of the molecular components. This approach, however, does not only change hydrogel mechanics, but also the microstructure, which in turn alters the macroscopic properties of the gel. Here, the Hofmeister effect is used to change the thermoresponsiveness of polyisocyanide hydrogels. In contrast to previous Hofmeister studies, the effect is used to change the phase transition temperatures and to tailor the mechanics of the thermoresponsive (semiflexible) polymer gels. It is demonstrated that the gel stiffness can be manipulated over more than two orders of magnitude by the addition of salts. Surprisingly, the microstructure of the gels does not change upon salt addition, demonstrating that the Hofmeister effect provides an excellent route to change the mechanical properties without distorting other influential parameters of the gel.

Thermoresponsive Properties of Copolymer Gels Induced by Appropriate Hydrophilic/Hydrophobic Balance of Monomer Combination

SummaryThe novel thermoresponsive polymer gels were found to be designed by copolymerization of hydrophilic and hydrophobic monomers. Thermoresponsive properties of these novel copolymer gels could be easily regulated by the monomer structures and the feed ratio. First, we copolymerized hydrophilic N,N‐dimethylacrylamide (DMAAm) and hydrophobic N‐n‐butylacrylamide (NBAAm) in various feed ratio, and found that certain compositions (DMAAm : NBAAm = 70 : 30 ∼ 40 : 60) gave the thermoresponsive gels with sharp volume phase transition. It was because of appropriate hydrophilic/hydrophobic balance in the network as same as poly(N‐isopropylacrylamide) gel, in which the balance of hydrophilic amide group and hydrophobic isopropyl group produces thermoresponsive property. Then, we examined the effect of comonomer structures on thermoresponsive behavior of the copolymer gels by utilizing butyl acrylamide isomers (s‐butyl, i‐butyl, and t‐butyl) as hydrophobic component. As a result, all the gels copolymerized by butylacrylamide having isomeric butyl groups with DMAAm were found to show the thermoresponsive properties such as sharp change of the degree of swelling and collapsed temperature, which would be related to the hydration structure of water.

Forces on an attractive surface generated from a thermoresponsive polymer gel

Interaction between polymers and soft-matter surfaces in the biological cell is a common yet incompletely understood phenomenon. This work investigates a generic situation where a thermoresponsive polymer gel is placed in the vicinity of an adsorbing surface, and starts contracting. The force is mediated by polymer chains that partially attach to the surface and partially to the contracting gel. The main goal was to understand how the force generated by the transforming polymer gel depends on key parameters that describe the system, most importantly, the concentration of the polymer, the length of the force-mediating polymer, and the the distance between the surface and the outer border of the contracting polymer gel. The key result of the paper is the Laplace transform (with regard to the polymer length) of the pulling force expression. Analytical approximations for the force have been obtained, and the exact expression for the pulling force is presented for the situation when the gel starts contracting. In depth analysis of the force behavior revealed several phases adopted by the polymer during the gel contraction.

The Non‐effect of Polymer‐Network Inhomogeneities in Microgel Volume Phase Transitions: Support for the Mean‐Field Perspective

Thermoresponsive polymer gels exhibit pronounced swelling and deswelling upon changes in temperature, making them attractive for applications in sensing and actuation. This volume phase transition can be discussed in terms of mean‐field theoretical pictures to assess at which conditions it occurs continuously or discontinuously. However, this treatment disregards static nano‐ and micrometer‐scale inhomogeneities in gel polymer networks, which are a common feature of these materials. To check for the impact of such structural complexity, droplet‐based microfluidics are used to fabricate sub‐millimeter‐sized gel particles that exhibit critical compositions at the border between continuous to discontinuous volume phase transitions, along with determined static spatial polymer‐network heterogeneity on the nano­meter and micrometer length scales, which is characterized by low‐field NMR. These different microgels are then used to study their swelling and deswelling volume phase transitions from a sub‐millimeter perspective. In this investigation, microgel particles with similar content of crosslinker exhibit similar swelling and deswelling, independent of their extent of static polymer‐network inhomogeneity, in agreement with mean‐field theoretical predictions. image

Impact of Polymer Network Inhomogeneities on the Volume Phase Transition of Thermoresponsive Microgels

Thermoresponsive polymer gels exhibit pronounced swelling and deswelling upon changes in temperature, rendering them attractive for various applications. This transition has been studied extensively, but only little is known about how it is affected by nano- and micrometer-scale inhomogeneities in the polymer gel network. In this work, droplet microfluidics is used to fabricate microgel particles of strongly varying inner homogeneity to study their volume phase behavior. These particles exhibit very similar equilibrium swelling and deswelling independent of their inner inhomogeneity, but the kinetics of their volume phase transition is markedly different: while gels with pronounced micrometer-scale inhomogeneity show fast and affine deswelling, homogeneous gels shrink slowly and in multiple steps.

Ionic Conductivity through Thermoresponsive Polymer Gel: Ordering Matters

Thermoreversible polymer gel has been prepared using PEO-PPO-PEO block copolymer (Pluronic F77) which self-assembles into different microcrystalline phases like cubic, 2D-hexagonal, and lamellar. Addition of electrolyte (LiI/I(2)) converts the gel into a polymer gel electrolyte (PGE) which exhibits microphase-dependent ionic conductivity. The crystalline phases have been identified by SAXS as a function of the polymer concentration. It is found that the optimum value for the ionic conductivity (≈1 × 10(-3) S x cm(-1)) is achieved in the Im3m phase due to faster diffusion of ions through the 3D-interconnected micellar nanochannels. This fact is further supported by FTIR study, ionic transference number, and diffusion coefficient measurements.

Thermo- and pH-Responsive Poly(A-ProOMe)-graft-poly(AAc) Membrane for Selective Separation of Metal Ions

We investigated the permeation behavior of Li, Co, and Ni ions through thermo- and pH-responsive gel membranes, which were prepared by γ-ray grafting of pH-responsive poly(acrylic acid) (poly(AAc)) onto a thermo-responsive polymer gel of acryloyl-L-proline methyl ester (A-ProOMe). Using 15% AAc grafted membranes, the permeation constants of Li ions are 2.8 and 3.5 times higher than those of Co and Ni ions in a pH 6.0 buffer solution at 30 °C. These ratios are two and three times higher than those of 5 and 43% grafted gel membranes, respectively. By comparison with the permeation of metal ions through the non-thermo-responsive porous polyethylene membranes grafted with AAc chains or random copolymer gel membranes (poly(A-ProOMe-co-AAc)), it is clear that the structure in which adjacent carboxyl groups of poly(AAc) are surrounded by thermo-responsive A-ProOMe matrix causes selective permeability of Li ion over Co and Ni ions. The distributions of Co and Ni ions in the microscopic structures clearly show that the structure consisting of flexible chains of the carboxyl groups grafted onto the thermo-response gel membrane plays a decisive role in the superior selective permeation of a Li ion.