Gas Chromatographic Study of the Interactions in Styrene-Dimethylsiloxane Block Copolymers and Blends

Galin, Monique; Rupprecht, M. C.

doi:10.1021/ma60069a033

Cited by 37 publications

(11 citation statements)

References 9 publications

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“…Chromatographic columns of PS and of 4-VP homopolymer were also prepared for use in this part of the work as controls. In part 2 of the study, involving polymers with various S-4VP block lengths, the quantity of supported polymer was constant at 6 ± 0.5 wt %, in line with literature recommendations [ 13] for optimum data significance. Chromatographic data were obtained with a Perkin-Elmer Sigma 2 apparatus, equipped with a hot wire detector.…”

Section: Methodssupporting

confidence: 66%

Surface properties of some styrene/vinyl pyridine diblock polymers adsorbed on rutile

Bosse

Eisenberg

Deng

et al. 1993

Journal of Adhesion Science and Technology

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Section: Methodssupporting

confidence: 66%

Surface properties of some styrene/vinyl pyridine diblock polymers adsorbed on rutile

Bosse

Eisenberg

Deng

et al. 1993

Journal of Adhesion Science and Technology

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“…The Xi(23) values are systematically slightly lower than the calculated values, assuming simple additivity of the contribution of the two blocks which is observed when macroscopic phase separation occurs between very large domains. 30 Rough X23 values were tentatively estimated by using the same equation as previously used for the liquid state. Most of them lie within the range 0.3-0.5 but they may reach a higher value of about 1.2 for the two copolymers of lowest PEO content studied with n-heptane as a probe, a selective solvent for PDMS.…”

Section: Resultsmentioning

confidence: 99%

Structural and thermodynamic study of dimethylsiloxane-ethylene oxide PDMS-PEO-PDMS triblock copolymers

Galin¹,

Mathis²

1981

Macromolecules

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Linear triblock dimethyls iloxane-ethylene oxide PDMS-PEO-PDMS copolymers have been synthesized by hydrosilation polycondensation of a, -diallylpoly(ethylene oxide) (Mn = 6 X 10s and 10 X 103) and a,o!-dihydro(polydimethylsiloxane) (Mn = (1-4.5) X 103). Studies by dilatometry, differential scanning calorimetry, and X-ray scattering have shown that the copolymers are characterized by a periodic organization in lamellae or hexagonal cylindrical structures according to composition. PEO crystallizes within its own domains, with specific features such as a lower degree of crystallinity, a lower melting point with respect to that of the PEO precursor, and crystallinity independent of thermal conditions. Gas chromatography has allowed a semiquantitative estimation of the xpdms-peo interaction parameter and its dependence on temperature and composition. The values in the range 0.4-1.1 are in good agreement with the high incompatibility of the PDMS and PEO chains.

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“…This is expected because a much higher cooperative interaction was observed for the retention of these probes on random copolymers, as given in Figure 4, although the interaction is through bulk retention, Kb, in this case. The interaction en- 3 and a lower 11H in random copolymers as compared to the homopolymers, as dicussed above.…”

Section: Resultsmentioning

confidence: 86%

“…In general, the gas chromatographic retention of a probe by a polymer is due to two mechanisms, absorption into the polymer bulk phase and adsorption onto the polymer surface, so that 1 Inverse Gas Chromatography on Graft and Random Copolymers (2) or (3) where Kb is the partition coefficient of a probe between polymer bulk and gas phase, K.,,, that between polymer surface and gas phase, w, the polymer loading weight and A, the surface area of the polymer. In the case of a predominant bulk absorption mechanism, Vg 0 can be put equal to Kb which can be expressed approximately by the glc theory as follows.…”

Section: Theoretical Considerationmentioning

confidence: 99%

Inverse Gas Chromatography on Graft and Random Copolymers of Styrene and 2-Hydroxyethyl Methacrylate

Ito

Masuda

Shintani

et al. 1983

Polym J

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ABSTRACT:Inverse gas chromatography (IGC) was applied to amphiphilic graft copolymers of poly(2-hydroxyethyl methacrylate) (PHEMA) with polystyrene (PSt) branches using various probes at 160°C. Retention oftetradecane or amylbenzene, which selectively interacts only with PSt phase, suggested that a microphase inversion occurs around 20-30wt% PSt, below which PSt segments constitute a discontinuous phase (islands). Rather nonselective probes such as dimethylformamide and 2-(2-methoxyethoxy)ethanol showed a retention which exceeds that expected from a simple additive relation, suggesting a considerable contribution of their interaction with the interface of the microphase-separated domains. In contrast, random copolymers showed a retention behavior as expected for a statistical distribution of the monomer units. General discussion is given on IGC as a means of characterizing binary polymer systems.KEY WORDS Inverse Gas Chromatography I Amphiphilic Graft Copolymer I 2-Hydroxyethyl Methacrylate I Styrene I Microphase Separation I Morphology I Selective and Nonselective Probes I Inverse gas chromatography (IGC) has been developed by Guillet and others1.2 as a simple and convenient method for evaluating various properties of polymers such as melting point (Tm), glasstransition point (Tg), crystallinity, interaction parameter, and solubility parameter. In principle, it relies on the interaction of an appropriate volatile compound as a probe with a target polymer as a stationary phase in conventional gas chromatography. Since any change in polymer phase would be reflected in the retention behavior of a probe, IGC also appears to be useful as a method for examining a multi-phase structure in block or graft copolymers and in polymer blends, in addition to being a simple method of evaluating their interaction with the probe. Galin and Rupprecht 3 investigated the retention of decane on polystyrene (PSt)-polydimethylsiloxane (PDMS) block copolymers to estimate the domain size of PSt. Ward et a/. 4 similarly evaluated the morphology of PDMSbisphenol A polycarbonate block copolymers and blends. Decane as a probe was assumed in these cases to interact independently with the PDMS matrix and surface (interface) of PSt-or polycarbonate domains at a temperature below their Tg. Suzuki et a/. 5 studied the surface morphology of PSt-poly(ethylene oxide) blend by following the retention behavior of octane in comparison with scanning electron-microscope observation.We also examined a retention of dodecane on PSt-polytetrahydrofuran (PTHF) block copolymers6 and on poly(methyl methacrylate) (PMMA}-poly(stearyl methacrylate) (PSMA) graft copolymers7 to show that PTHF or PSMA segments, which have a lower Tm and a lower surface-energy, tend to make a continuous phase as compared to PSt or PMMA segments, respectively. In general, the IGC method may be expected to give more clear-cut and interesting information on the morphology of these multi-phase polymer systems by analyzing the retention behavior of several probes which may interact selec...

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Gas Chromatographic Study of the Interactions in Styrene-Dimethylsiloxane Block Copolymers and Blends

Cited by 37 publications

References 9 publications

Surface properties of some styrene/vinyl pyridine diblock polymers adsorbed on rutile

Surface properties of some styrene/vinyl pyridine diblock polymers adsorbed on rutile

Structural and thermodynamic study of dimethylsiloxane-ethylene oxide PDMS-PEO-PDMS triblock copolymers

Inverse Gas Chromatography on Graft and Random Copolymers of Styrene and 2-Hydroxyethyl Methacrylate

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