Guest exchange process in syndiotactic polystyrene thin films measured by ATR-FTIR spectroscopy

Uda, Yukihiro; Kaneko, Fumitoshi; Kawaguchi, Tatsuya

doi:10.1016/j.polymer.2004.02.004

Cited by 35 publications

(26 citation statements)

References 35 publications

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“…21 However, we should be careful when comparing diffusion coefficients obtained under different experimental conditions as suggested by Musto et al 36 The diffusion of penetrant in the amorphous region is greatly influenced by the plasticizing effect. Therefore, the D a depends significantly on the kind and concentration of penetrant.…”

Section: Estimation Of Diffusion Coefficientsmentioning

confidence: 99%

“…The IR data in our preceding study suggested that the guest exchange takes place in two steps: a rapid replacement of the sorbate with desorbate in the amorphous region in initial stage and a subsequent slow guest exchange in the crystalline region. 21 However, we could not obtain definite evidence of the above mechanism, since it was impossible to determine the ratio in real time at which the sorbate and desorbate molecules were distributed between the amorphous and crystalline regions.…”

Section: Introductionmentioning

confidence: 96%

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Guest Exchange Mechanism in the Clathrate Phase of Syndiotactic Polystyrene

2005

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The guest exchange mechanism in the clathrate phase of syndiotactic polystyrene (sPS) was investigated by ATR-FTIR spectroscopy utilizing the selectivity of the sPS crystalline region about the conformation of 1,2-dichloroethane (DCE). 1,2-Dichloroethane (h-DCE) and its deuterated compound (d-DCE) were used as guests to analyze the sorption behavior of the sorbate molecules and the desorption behavior of the guest molecules stored in the crystalline region beforehand, simultaneously. The spectral changes on the exposure of an sPS film containing d-DCE to h-DCE vapor were followed, and the information about the guest exchange processes in both the crystalline and amorphous regions were obtained. In the earliest stage, the exchange occurred mainly in the amorphous region, while the exchange in the crystalline region proceeded gradually for a long time. On the basis of this finding, the diffusion coefficients of DCE molecules in the crystalline and amorphous regions were estimated.

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Section: Estimation Of Diffusion Coefficientsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 96%

Guest Exchange Mechanism in the Clathrate Phase of Syndiotactic Polystyrene

2005

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“…[7] However, the properties of the amorphous region will have an influence on the sorption process, since solvent molecules pass through the amorphous region to reach the crystalline region. Contrary to the d e form, which is treated by an extraction procedure, the amorphous region of the d form film contains a small amount of chloroform used as casting solvent, and this residual chloroform acts as a plasticizer; [13,15] the higher the mobility of the amorphous region, the more easily the sorbate molecules diffuse into it. This effect would assist the transport of the sorbate to the crystalline region.…”

Section: Ease Of Solvent Sorption Into the D Formmentioning

confidence: 99%

“…The replacement of the molecules confined in the cavities of the d form with a different kind of molecule was first observed in an X-ray study by Chatani et al; [12] this phenomenon was later confirmed by IR spectroscopy. [13] This process proceeds smoothly, and the molecules stored in the cavities are released much faster in the guest-exchange process than in an ordinary desorption process.…”

Section: Introductionmentioning

confidence: 99%

Selective Guest Uptake from Solvent Mixtures in the Clathrate Phase of Syndiotactic Polystyrene

Uda

Kaneko

Kawaguchi

2004

Macromol. Rapid Commun.

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Summary: Selective absorption uptake during the guest‐exchange processes in the δ form of syndiotactic polystyrene (sPS) was confirmed by IR spectroscopy. When films of the δ form were immersed in hexane/decane or chloroform/decane mixtures, decane molecules were incorporated preferentially in the δ form. Sorbate uptake by the δ form was greatly accelerated when the sorbate was mixed with a solvent penetrable to the amorphous region of sPS.Concentration changes in a δ‐form film during sorption processes: sorption of a chloroform(D)/decane(H) mixture (1:1 molar ratio).magnified imageConcentration changes in a δ‐form film during sorption processes: sorption of a chloroform(D)/decane(H) mixture (1:1 molar ratio).

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“…However, some guest molecules can be easily exchanged with particular solvents by keeping the samples in the corresponding solvent atmosphere [55][56][57][58][59][60][61][62]. The rate of guest exchange depends on the interaction between the polymer and the guest and also on the size of the guest molecule [57].…”

Section: Introductionmentioning

confidence: 99%