Effect of mixed solvent on solution properties and gelation behavior of poly(vinyl alcohol)

Hong, Shi-Jie; Hong, Po‐Da; Chen, Jyh‐Chien; Shih, Kan-Shan

doi:10.1016/j.eurpolymj.2009.01.005

Cited by 19 publications

(12 citation statements)

References 34 publications

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“…12 Therefore, if we continuously increase the methanol content at a constant temperature (e.g., 20 °C), PNIPAM would undergo a reentrant coilto-globule-to-coil phase transition, 24,25,31 which can even be used to purify PNIPAM in synthesis. 32 Interestingly, similar phenomena can also be found in water/organic solvent mixtures of poly-(vinyl alcohol) (PVA), 33 poly(N-vinylpyrrolidone) (PVP), [34][35][36] poly(N-vinylcaprolactam) (PVCL), 36 poly(vinyl methyl ether) (PVME), 22,37 poly(N,N-dimethylacrylamide) (PDMAM), 38 poly-(N-(2-ethoxyethyl)acrylamide) (PEoEA), 39 poly(N,N-diethylacryamide) (PDEA) 40 as well as other oligomeric polyacrylamides. 41 Up to the present, plenty of investigations have been devoted to elucidate the nature of cononsolvency of PNIPAM in water/ methanol mixture, including some structurally confined systems, e.g., PNIPAM gels, [42][43][44][45][46] PNIPAM brushes 47 and interfaces.…”

Section: Introductionmentioning

confidence: 72%

“…Therefore, if we continuously increase the methanol content at a constant temperature (e.g., 20 °C), PNIPAM would undergo a reentrant coil-to-globule-to-coil phase transition, ,, which can even be used to purify PNIPAM in synthesis . Interestingly, similar phenomena can also be found in water/organic solvent mixtures of poly(vinyl alcohol) (PVA), poly( N -vinylpyrrolidone) (PVP), − poly( N -vinylcaprolactam) (PVCL), poly(vinyl methyl ether) (PVME), , poly( N , N -dimethylacrylamide) (PDMAM), poly( N -(2-ethoxyethyl)acrylamide) (PEoEA), poly( N , N -diethylacryamide) (PDEA) as well as other oligomeric polyacrylamides …”

Section: Introductionmentioning

confidence: 92%

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Role of Water/Methanol Clustering Dynamics on Thermosensitivity of Poly(N-isopropylacrylamide) from Spectral and Calorimetric Insights

Sun

2010

Macromolecules

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The role of water/methanol clustering dynamics on thermosensitivity of poly(N-isopropylacrylamide) (PNIPAM) chains in concentrated solutions (10 wt %) is investigated by turbidity, FT-IR and calorimetric measurements through point-by-point comparison. FT-IR spectral variations show that PNIPAM−methanol interactions are largely weakened and PNIPAM chains are more collapsed in water/methanol mixture (methanol volume fraction x m = 0.17) than in pure water because of the formation of large water/methanol clusters, which, meanwhile, causes the decrease of hydration sites. On the other hand, weak hysteresis and excess recovery phenomena in the phase transition process can also be observed with addition of methanol to PNIPAM aqueous solution due to the existence of water/methanol clustering dynamics. Two-dimensional infrared correlation spectroscopy and calorimetric analysis finally conclude that the role of water/methanol clustering dynamics is mainly embodied in the inhibition of the hydration process of PNIPAM chains which shows a faster thermal response than hydrogen bonding association.

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Section: Introductionmentioning

confidence: 72%

Section: Introductionmentioning

confidence: 92%

Role of Water/Methanol Clustering Dynamics on Thermosensitivity of Poly(N-isopropylacrylamide) from Spectral and Calorimetric Insights

Sun

2010

Macromolecules

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“…This phenomenon has been widely applied in the physicochemical, green chemical, and pharmaceutical industries 27,31 . Poly(vinyl alcohol) (PVA) can form a hydrogel in a mixture of water and dimethyl sulfoxide (DMSO) via the cononsolvency effect, attributed to the strong interaction between water and DMSO molecules 28,32‐35 . On the other hand, the strong interaction between water and DMSO molecules makes the water/DMSO binary system have lower freezing temperature than the pure solvents do 36,37 .…”

Section: Introductionmentioning

confidence: 99%

Rapid and scalable fabrication of ultra‐stretchable, anti‐freezing conductive gels by cononsolvency effect

Alsaid

Yao

et al. 2021

EcoMat

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With the emergence of soft electronic devices, the requirements for conductive soft materials are unprecedentedly high. Among various soft materials, hydrogels are gaining tremendous attention for their superior softness, wetness, responsiveness, and biocompatibility. However, hydrogels inevitably lose elasticity and ionic conductivity at subzero temperature because of water freezing in the polymer matrices, severely limiting applications at low temperatures. Herein, we propose a rapid fabrication strategy to produce anti‐freezing conductive gels with poly(vinyl alcohol) on a large scale within minutes (vs hours/days in conventional methods) using a water/DMSO binary liquid system, which serves as gelation inducer via cononsolvency and anti‐freezing solvents simultaneously. The gel with 60 wt% DMSO shows the best anti‐freezing performance, remaining unfrozen at temperatures lower than −50°C, while also maintaining the highest mechanical properties with a tensile strength of 1.1 MPa, toughness of 10.9 MJ/m3, and elongation of 1500% outperforming the most previous reports. After incorporating H2SO4, the gels exhibit a high ionic conductivity of 5.25 S/m and maintain 1.65 S/m even at −50°C. Furthermore, an all‐in‐one supercapacitor is fabricated to demonstrate the potential of the anti‐freezing gel in soft device applications with good performance at subzero temperatures. A full recyclability of the material was also demonstrated.

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“…Biocompatibility and biodegradability are two promising features of PVA, an environment-friendly synthetic polymer. 2 The structure and physical behavior characteristics of aqueous solutions of PVA were studied previously using experimental techniques such as static and dynamic light scattering, 3,4 viscosity measurements, 5,6 dielectric relaxation studies, 7 and computational methods such as molecular dynamics simulation. 8,9 It was observed that the solution properties of PVA depend on factors such as degree-ofhydrolysis of the polymer, concentration of polymer, temperature, pressure, and presence of electrolytes in solution.…”

Section: Introductionmentioning

confidence: 99%

“…The structure and physical behavior characteristics of aqueous solutions of PVA were studied previously using experimental techniques such as static and dynamic light scattering, , viscosity measurements, , dielectric relaxation studies, and computational methods such as molecular dynamics simulation. , It was observed that the solution properties of PVA depend on factors such as degree-of-hydrolysis of the polymer, concentration of polymer, temperature, pressure, and presence of electrolytes in solution . PVA in aqueous solutions at room temperature is not molecularly dispersed due to its semicrystalline nature with the aqueous solution containing microgel particles even under highly dilute concentration conditions .…”

Section: Introductionmentioning

confidence: 99%

Factors Responsible for the Aggregation of Poly(vinyl alcohol) in Aqueous Solution as Revealed by Molecular Dynamics Simulations

Kurapati

Natarajan

2020

Ind. Eng. Chem. Res.

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Molecular dynamics simulations are used to study the structure and dynamics of poly(vinyl alcohol) and water in aqueous solution as a function of concentration at different temperatures in the range of 278–338 K. Simulations were performed using multiple oligomeric chains for facilitating interchain interactions as well as a direct comparison with experimental data. PVA chains fold and bundle up to form an aggregate in solution. The intermolecular spatial distributions show the structure of aggregate to be ordered. PVA chains show a high tendency to form intrachain hydrogen bonds between adjacent repeating units, instead of interchain H-bonds, indicating hydrophobic effect as the major driving force for aggregate formation. At all temperatures, the conformations of a single PVA chain by itself in solution are unstable, going back and forth between extended and folded states. However, interchain interactions among PVA chains in the aggregate stabilize the folded conformation. An increase in temperature results in faster motions and an increase in concentration results in slower dynamics. At higher concentration, the chains adopt a single folded state independent of temperature so that there is an insignificant effect on R g. The competition between the formation of various hydrogen bonds such as intrachain, interchain, and PVA–water is the key to understand the solvation behavior of PVA. The activation energy for the conformational transition between the trans and gauche states of backbone dihedrals obtained from the simulations is 15.73 kJ/mol, which is close to the value of 13.4 kJ/mol obtained from experiments for 15 wt % PVA solution. The hydrophobic effect rather than interchain PVA hydrogen bonding is the major driving force for the aggregation of PVA in water.

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Effect of mixed solvent on solution properties and gelation behavior of poly(vinyl alcohol)

Cited by 19 publications

References 34 publications

Role of Water/Methanol Clustering Dynamics on Thermosensitivity of Poly(N-isopropylacrylamide) from Spectral and Calorimetric Insights

Role of Water/Methanol Clustering Dynamics on Thermosensitivity of Poly(N-isopropylacrylamide) from Spectral and Calorimetric Insights

Rapid and scalable fabrication of ultra‐stretchable, anti‐freezing conductive gels by cononsolvency effect

Factors Responsible for the Aggregation of Poly(vinyl alcohol) in Aqueous Solution as Revealed by Molecular Dynamics Simulations

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