Inverse gas chromatography study of polyvinylacetate–solvent and polyethylene–solvent systems

Camacho, Javier; Díez, Eduardo; Gómez, L J García; Ovejero, Gabriel

doi:10.1002/pen.24189

Cited by 5 publications

(17 citation statements)

References 24 publications

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“…To characterize the structure of the studied polymers, DSC analyses were performed. The DSC curves of PE, PVAc and EVA polymers can be also found in previous works …”

Section: Experimental Data and Methodologysupporting

confidence: 54%

“…On the other hand, at temperatures higher than T g , the retention volume is a measurement of the interaction of the solvent with the bulk polymer in liquid state; in this situation the diffusion of the solvent in the polymer is rapid enough so the normal gas chromatographic behaviour can be observed (the retention volume decreases linearly with increasing temperature). In previous publications, this decreasing linear zone was observed for association solvents and for polar solvents, starting at least from 60 °C, but it was not observed for dispersion solvents. For this reason, the infinite dilution activity coefficients and the Flory–Huggins parameters were only calculated in the temperature range from 60 to 80 °C and only for polar‐type and dispersion‐type solvents, except for cyclohexane.…”

Section: Experimental Data and Methodologymentioning

confidence: 61%

“…The Flory–Huggins parameters ( χ ) were taken from previous publications . In these sources, they were calculated with Eqn , from the values of infinite dilution activity coefficients, Ω 1 ∞ (which were previously calculated from retention volume values) following the inverse gas chromatography (IGC) basis:

χ = normalln ((), Ω_{1}^{\infty}) - ((), 1 - \frac{1}{r}) + normalln \frac{ρ_{1}}{ρ_{2}}

…”

Section: Experimental Data and Methodologymentioning

confidence: 99%

“…In this equation, r is the ratio between molar volume of the polymer and the molar volume of the solvent, and ρ 1 and ρ 2 are the solvent and polymer densities, respectively. The Flory–Huggins values are summarized in Tables and .…”

Section: Experimental Data and Methodologymentioning

confidence: 99%

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Hansen solubility parameter: from polyethylene and poly(vinyl acetate) homopolymers to ethylene–vinyl acetate copolymers

Camacho

Díez

Díaz

et al. 2017

Polymer International

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The Hansen solubility parameters (HSPs) of two ethylene–vinyl acetate (EVA) copolymers (with 18 and 33 wt% of vinyl acetate) and their corresponding homopolymers (polyethylene, PE, and poly(vinyl acetate), PVAc) have been studied at various temperatures, employing the previously obtained Flory–Huggins parameters. From these latter values, a procedure based on the Hansen solubility spheres theory was employed to determine the HSPs, as well as the radius of interaction. The procedure was validated with literature data, with deviations of around 3%. The HSP values (dispersion, polar and association terms, respectively, all in MPa1/2) at 333.15 K are 14.84, −3.88 and 1.78 for PE, 17.65, −1.24 and 2.76 for EVA410 (with 18 wt% of vinyl acetate), 17.52, 0.15 and 3.61 for EVA460 (with 33 wt% of vinyl acetate) and 19.45, 10.59 and 5.76 for PVAc. The main characteristic of the obtained HSP values is that the high polar term of PVAc tends to increase the solubility character of the pure PE, and thus the EVA copolymers, allowing them to solubilize dispersion and polar compounds. Finally, it was also demonstrated that it is possible to predict the HSPs of EVA copolymers using the vinyl acetate content and the HSPs of pure PE and PVAc as input data. © 2017 Society of Chemical Industry

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“…To characterize the structure of the studied polymers, DSC analyses were performed. The DSC curves of PE, PVAc and EVA polymers can be also found in previous works …”

Section: Experimental Data and Methodologysupporting

confidence: 54%

Section: Experimental Data and Methodologymentioning

confidence: 61%

χ = normalln ((), Ω_{1}^{\infty}) - ((), 1 - \frac{1}{r}) + normalln \frac{ρ_{1}}{ρ_{2}}

…”

Section: Experimental Data and Methodologymentioning

confidence: 99%

Section: Experimental Data and Methodologymentioning

confidence: 99%

See 2 more Smart Citations

Hansen solubility parameter: from polyethylene and poly(vinyl acetate) homopolymers to ethylene–vinyl acetate copolymers

Camacho

Díez

Díaz

et al. 2017

Polymer International

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“…It can be observed the expected best interactions for the cyclohexane probe, due this solvent presents the lowest overall Flory-Huggins parameters (and the mass-based infinite dilution solvent activity coefficients), following by vinyl acetate, and finally methanol. These overall and amorphous Flory-Huggins parameters are plotted together with overall FloryHuggins parameters previously reported in literature for these systems [21,22], showing highly satisfactory agreement. Polym.…”

Section: Retention Volumesmentioning

confidence: 58%

Bulk polymer/solvent interactions for polyethylene and EVA copolymers, below their melting temperatures

2016

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In this work, the Flory-Huggins parameters corresponding to the amorphous phase of a polyethylene (PE) and two ethylene-vinyl acetate (EVA) copolymers (with 18 and 33 % vinyl acetate content, respectively) samples, with different solvents have been determined below the melting temperature of the polymers, in order to quantify the bulk interactions of these polymer/solvent systems. The employed solvents were a dispersion solvent (cyclohexane), a polar solvent (vinyl acetate) and an association solvent (methanol). Initially, the inverse gas chromatography measurements allowed obtaining the retention volumes, activity coefficients and overall Flory-Huggins parameters of every polymer/solvent system. According to these parameters, in all cases, the more compatible solvent was cyclohexane, so it was selected as the probe to calculate the percentages of crystallinity at room temperature, whose results were in agreement the literature data (35 % for PE, 29 % for EVA18, and 12 % for EVA33). The percentage of crystallinity allowed determining the amorphous Flory-Huggins parameters which are the ones which take into account just the bulk interactions in a polymer/solvent mixture. The Flory-Huggins parameter results show that, to accurately study the vapor-liquid equilibrium between a polymer and a solvent (bulk interactions), when the range of studied temperatures is below the melting point of the polymer, it is crucial to calculate the amorphous contribution (v amorphous ) on the overall FloryHuggins parameter. In the case of this study, the lower the vinyl acetate content (higher crystallinity), the higher the difference between the overall and amorphous Flory-Huggins parameters is. Analyzing the interactions between the three polymeric materials and the solvents it can be noticed that, for the most compatible & Eduardo Díez solvent (cyclohexane), v amorphous represents the less contribution, or the highest correction, to the overall Flory-Huggins parameter (around 50 % for PE and EVA18, and 79 % for EVA33, the less crystalline polymer).

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A new methodology to determine sorption curves from Flory Huggins parameters measured at solvent and polymer infinite dilution

Camacho

Díez

Ovejero

2016

European Polymer Journal

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Inverse gas chromatography study of polyvinylacetate–solvent and polyethylene–solvent systems

Cited by 5 publications

References 24 publications

Hansen solubility parameter: from polyethylene and poly(vinyl acetate) homopolymers to ethylene–vinyl acetate copolymers

Hansen solubility parameter: from polyethylene and poly(vinyl acetate) homopolymers to ethylene–vinyl acetate copolymers

Bulk polymer/solvent interactions for polyethylene and EVA copolymers, below their melting temperatures

A new methodology to determine sorption curves from Flory Huggins parameters measured at solvent and polymer infinite dilution

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