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Preparative and analytical aspects of polymer fractionation

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Fortschritte der Hochpolymeren-Forschung

Part of the book series: Advances in Polymer Science ((POLYMER,volume 7/1))

Abstract

Fractionation has been, and probably still is the most frequently used experiment in polymer research. In spite of the abundant literature describing the great efforts devoted to the subject, the methods and techniques developed so far do not yield quite satisfactory results. This holds both for preparative and for analytical fractionation.

The theoretical analyses described here reveal that it should be possible to prepare large fractions (about 100 g) of very narrow distribution (M w /M n ≈ 1.01), albeit that the relevant techniques have not yet, or only partly, been put into practice.

Reliable determination of the differential molecular weight distribution by means of the classical precipitation or extraction procedures is not possible. In the evaluation of the fractionation data problems are encountered that can, in fact, only be solved satisfactorily if the distribution is known beforehand.

An alternative analytical method, based upon a detailed analysis of phase relationships, is still in an early stage of development. Being an absolute procedure it could be useful for supporting other absolute data, e.g. those obtained from the sedimentation-diffusion equilibrium in the ultracentrifuge.

Double-primed quantities refer to the concentrated phase, single-primed ones to the dilute phase

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Abbreviations

a:

Mz/Mw

b:

Mw/Mn

en :

Huggins' criterion of fractionation efficiency (Eqs. (14) and (15))

fn :

efficiency criterion (Eqs. (16) and (17))

ΔG:

free enthalpy (Gibbs free energy) of mixing

g:

interaction parameter

g 01 :

solvent-polymer interaction parameter

g 02 :

solvent-precipitant interaction parameter

g 12 :

polymer-precipitant interaction parameter

M:

molecular weight

Mn,Mw,Mz :

number-, weight- and z-average molecular weight

m:

relative chain length (Eq. (1))

mn, mw, mz :

number-, weight- and z-average relative chain length

R:

gas constant

r:

V′/V″

s 0 :

relative chain length of solvent (Eq. (3))

s:

relative chain length of non-solvent (Eq. (4))

T:

absolute temperature

V″, V′:

volumes of the concentrated and dilute phases

w (M):

differential weight distribution

W (M):

integral weight distribution

W″:

mass of fraction in concentrated phase

W:

mass of whole polymer

wi :

mass of polymer species i

x:

W″/W = relative fraction size

ϕ 0 :

volume fraction of solvent

ϕi :

volume fraction of polymer species i

ϕ:

∑ϕ i =whole polymer voluem fraction

ϕe :

critical volume fraction

ϕih :

threshold concentration

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  1. Central Laboratorium, N. V. Nederlandse Staatsmijnen/DSM, Geleen, The Netherlands

    R. Koningsveld

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Koningsveld, R. (1970). Preparative and analytical aspects of polymer fractionation. In: Fortschritte der Hochpolymeren-Forschung. Advances in Polymer Science, vol 7/1. Springer, Berlin, Heidelberg. https://doi.org/10.1007/BFb0051108

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  • DOI: https://doi.org/10.1007/BFb0051108

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