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Rapid detection of compositional drift of polydisperse copolymers using thermal field-flow fractionation and multi-angle light scattering

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Summary

The use of thermal field-flow fractionation (ThFFF) with multi-angle light scattering (MALS) for the rapid detection of compositional heterogeneity in random copolymers is demonstrated. Soret coefficients were directly calculated from the ThFFF retention times while the MALS detector provided the polymer's radius of gyration (R g) distribution. FromR g, the diffusion coefficient (D) could be calculated and this allowed, in combination with the Soret coefficient, the calculation of the thermal diffusion coefficient (D T). It was shown that theD T distribution can serve as a measure for the chemical composition distribution of random styrene acrylonitrile copolymers. Comparison of ThFFF-MALS results with literature data from ThFFF-hydrodynamic chromatography (HDC) cross-fractionation experiments showed a fair agreement.

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Abbreviations

c :

concentration kg m−3

c inj :

sample concentration kg m−3

D :

diffusion coefficient m2 s−1

D T :

thermal diffusion coefficient m2 s−1 K−1

K :

optical constant

M :

molecular mass kg mol−1

M w :

weight-average molecular mass kg mol−1

n :

refractive index

R:

retention ratio

R (Φ):

excess Rayleight ratio m−1

R g :

radius of gyration m

R h :

hydrodynamic radius m

t r :

retention time s

t 0 :

void time s

T c :

cold wall temperature K

ΔT :

temperature drop K

ϕ:

scattering angle rad

λ:

dimensionless retention parameter

λ l :

wavelength m

μ:

polydispersity

ϕ:

conversion factor

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Authors and Affiliations

  1. Laboratory for Analytical Chemistry, University of Amsterdam, Nieuwe Achtergracht 166, 1018 WV, Amsterdam, The Netherlands

    E. P. C. Mes, R. Tijssen & W. Th. Kok

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  1. E. P. C. Mes
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  2. R. Tijssen
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  3. W. Th. Kok
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Mes, E.P.C., Tijssen, R. & Kok, W.T. Rapid detection of compositional drift of polydisperse copolymers using thermal field-flow fractionation and multi-angle light scattering. Chromatographia 50, 45–51 (1999). https://doi.org/10.1007/BF02493616

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