British Polymer Journal 22 (1990) 255-259

Preferential Adsorption in
Polymer/Solvent-l /Solvent-2 Solutions
by Infrared Spectroscopy
Carmen Gonzalez, Fernando Zamora
Departamento de Ciencia y Tecnologia de Polimeros, Universidad de Pais Vasco,
Apdo. 1072, 20080-San Sebastian, Spain

Eva Gutierrez, Juan C. Ramirez & Luis M. Leon

Departamento de Quimica-Fisica, Universidad de Pais Vasco, Apdo. 644, 48080-Bilbao, Spain

(Received 2 May 1989; revised version received 27 June 1989; accepted 5 September 1989)

Abstract: I R spectroscopy is shown to be a suitable technique for preferential

adsorption studies in the following solvent- I/solvent-2/polynier systems: poly( N -
vinylcarbazole) and polyacenaphthene in nitrobenzene/dioxane, nitrobenzene/
tetrahydrofuran, and nitrobenzene/cyclohexanone. Values of the prcfercntial
adsorption parameters derived from the Schultz-Flory theory agree with those from
I R when both solvents in the ternary system are considered to be good solvents for
the polymer. In the systems studied, the relative adsorptions of solvent-1 and
solvent-2 by the polymer depend on the solvent mixture composition. The number
of adsorbed molecules and their performance are correlated with the ternary
interaction parameters, x , , ~ and
, the Mark-Houwink-Sakurada exponent, a'. The
adsorption changes observed are greater in those systems in which tetrahydrofuran
was present.

Key words: poly(N-vinylcarbazole), polyacenaphthene, preferential adsorption,

infrared spectroscopy.

INTRO D UCTlO N
Many attempts have been made to evaluate pre-
ferential adsorption coefficients both theoretically,
relating the preferential adsorption parameter with
interaction parameters,'32and experimentally, using
different experimental techniques according to the
chemical groups involved in the adsorption process.
Spectroscopic techniques such as nuclear magnetic
resonance NMR,3 infrared spectroscopy (IR)4 and
fluorescence5have often been used for this purpose.
In this paper we use IR spectroscopy to determine
the preferential adsorption parameter, b,, for
solvent- 1 in the solvent- l/solvent-2/polymer-3 sys-
tem, where
Y A
"1
b --in3
l-M,
Brifish Polymer Journal 0007-1641/90/$03~50 0 1990 Society of Chemical Industry. Printed in Great Britain
and in3is the molecular weight of the repeating unit,
M , is the molecular weight of the polymer, and x1 is
the moles excess of solvent- 1 per macromolecule,
which can be determined from the IR absorbance
difference between a solvent mixture and the same
solvent mixture with a polymer.
For a given solvent-l/solvent-2 mixture, A , is the
absorbance of an IR band of solvent-1 and A the
absorbance of the same band when a polymer is
present in such a solvent mixture. According to
Lambert-Beer's law:
A,, = ahc,
and
= abc
(')
b being the optical path length, a the absorptivity,
255
256 Carmen Gonzalez, Fernando Zamora, Eva Gutierrez, Juan C. Ramirez, Luis M . Lebn

and co and c, respectively, the solvent-1 con-
centration before and after the polymer is added to
the solvent mixture.
The amount (co-c) corresponds to the con-
centration of solvent-1 molecules removed from the
bulk solution and adsorbed on the polymer chain.
Values of (co - c) are positive when solvent-1
molecules are adsorbed, and negative when solvent-
1 is desorbed. If solvent-2 is able to interact
preferentially with the polymer, it should be reflected
in the IR spectrum. So, x1 in eqn (1)can be calculated
from the ratio x , = (co - c)/c,, cp being the polymer
concentration in the solvent mixture.
Alternatively, b , can be calculated from the
relationship given by Schultz and Flory:'
ation chromatography and viscometry using the
universal calibration method.
Solvent mixture compositions of 20, 40, 60 and
80% (v/v) in NB were prepared. The polymer
concentration was always 0.5% (w/v). The IR
spectrum of each solvent mixture and its corre-
sponding polymer/solven t mixture solution was
registered systematically in a Perkin-Elmer Spectro-
photometer model 1430 using a KBr liquid cell with
a fixed optical pathway of 2.4 x cm, which was
measured by the interference fringe technique. The
solvents used were spectroscopic grade.
RESULTS A N D DISCUSSION
A PNVC fraction with a weight-average molecular

hl
1111v3
=-4,42
Vl i(41-421x1.2 + x1,3 - / x 2 , 3 + ('-
141+ 4 2 - 2 x 1 . 2 4 1 4 2
(2)
')
I weight M , = 7.65 x lo5 and a PACE fraction with
M , = 4.43 x lo3 were selected for this study.
The adsorption band at 800cm-' for NB was

where u3 is the specific volume of the monomeric

unit, V , is the molar volume of solvent-1, 4, and 42
are the volume fractions (%v/v) of solvent-1 and
solvent-2, respectively, I = ( V1/ V,) is the ratio 2
[
1

between molar volume of solvent-1 and solvent-2,

and x1,2, x1,3 and x , , ~ are the corresponding
interaction parameters. and x 2 , 3 can be obtained
from eqn ( 3 ) if the respective Stockmayer-Fixman
parameters, B1,2 and B 2 , 3 have previously been
determined.

where N A is Avogadro's number, and i can be 1 or 2.

(3) -It
-2b
I
20
I
40
V
I
60
I
80
I
100

For our purpose we have chosen poly(N- +, We)

Fig. 1. Concentration of adsorbed molecules of nitrobenzene

vinylcarbazole) (PNVC)in mixtures of nitrobenzene (co - c) versus volume fraction of nitrobenzene, for PNVC in
(NB) as solvent-1 and dioxane (D), tetrahydrofuran mixtures: 0 NB/D; NB/THF; x NB/CH.
(THF) or cyclohexanone (CH) as solvent-2. In these
systems we have compared h , values obtained from
eqn (1) with those from eqn (2). Values of b , have
also been determined for polyacenaphthene (PACE)
in the same solvent mixtures by IR spectroscopy.
Previously, we reported results of preferential
adsorption of PNVC/solvent/non-solvent systems
by NMR' and IR spectroscopy7 in which the non-
solvent was adsorbed continuously by the polymer,
affecting its flexibility. Now we deal with the
performance of ternary systems, polymer/solvent/
solvent.

EXP E R IMENTA L -It

-2I
0
I
20
I
40
I
60 80
I 1
100
PNVC and PACE samples were synthesized cation- +,(%I
i ~ a l l y *and
. ~ submitted to fractional precipitation Fig. 2. Concentration of adsorbed molecules of nitrobenzene
from a 1% (w/v) benzene solution with methanol at (co - c) versus volume fraction of nitrobenzene, dl,for PACE in
298 K. Fractions were characterized by gel perme- mixtures: 0 NB/D; NB/THF; x NB/CH.

BRITISH POLYMER JOURNAL VOL. 22, NO. 3,1990

Preferential adsorption in polymerlsolvent-l/solvent-2 solutions 257

2o t
-20J
40f
0

n
-
-20

-40.

-6Oh
/

I I I I I
-20:
0 20 40 60 80 100 20 40 60 80 100
9, ( ' l o ) +, (*I.)
Fig. 3. Experimental values of the preferential adsorption Fig. 4. Experimental values of the preferential adsorption
parameter, b,, versus volume fraction of nitrobenzene, dl, for parameter, b,, versus volume fraction of nitrobenzene, $,, for
PACE in mixtures: A NB/D; NB/THF; 0 NB/CH. PNVC in mixtures: A NB/D; NB/THF; 0 NB/CH.
Theoretical values of b , , obtained by applying eqn (2), are
chosen because it does not overlap with other bands indicated also ( x - x ).
for this solvent. Polymer bands do not appear in the
spectra because the polymer concentration was too values agree with the experimental ones for NB/D
low. and NB/CH mixtures. In NB/THF mixtures they
Considering nitrobenzene as solvent-1, (co - c) is show similar variations but the number of adsorbed
the difference of the NB concentration in the bulk molecules is lower.
solution when polymer is absent and when it is In order to apply the relationship given in eqn (2),
present. Data of (co - c) versus solvent-1 compo- the interaction parameters x ~ , x1,3
~ , and ~ 2 . 3were
sition, +,, are plotted in Fig. 1 and Fig. 2 for PNVC calculated beforehand. The corresponding xi,3
and PACE, respectively. The rises and falls in the values between polymer and NB, D, THF or CH
plots of (co - c) versus 41 indicate a competitive were calculated using eqn (3) in which Bi,3 values
interaction process between the polymer and the two were obtained from intrinsic viscosity and molecular
solvents, since both can be adsorbed. weight data for PNVC in these so1vents.l0-l2 The
Figure 3 shows 6, values for PACE in three xi,3 values obtained are listed in Table 1. The three
solvent mixtures, and changes of adsorption of interaction parameters solvent-l/solvent-2, x1, 2 ,
solvent-1 in the presence of solvent-2 are shown as were calculated using the expression given by Blanks
an increase or decrease in b, values. However, the and Prausnitz:'
quantity of molecules adsorbed is quite different.
In Fig. 4 are plotted the b, values obtained for Vl , z A 1 ,a?
Xl,Z =
RT 4142 (4)
PNVC. A change in preferential adsorption is
observed in the three solvent mixtures when 4, is where Vl,2 is the molar volume of the solvent
around 50%. Many more molecules are involved in mixture, R is the gas constant, and T the tempera-
the adsorption phenomenon when THF is present. ture. A l , 2 may be expressed as
Values of 6, calculated from eqn (2) for PNVC
systems have also been included in Fig. 4. These

BRITISH POLYMER JOURNAL VOL. 22, NO. 3,1990

258 Curriteti Gonzdlez, Fernando Zamora, Eva Gutierrez, Juan C. Rarnirez, Luis M. Lrdn

polar and hydrogen bond interactions of solvent-1

and solvent-2 to the solubility parameter. These
values were calculated by adding group contri-
butions to data reported in Ref. 14. Table 2 shows
values for the three solvent mixtures.
The knowledge of ternary interaction parameters,
x ~ . given15
~ , by eqn (6) leads to knowledge of the
0.6

0.4

o.2-
- -
n
(a)

interaction degree between polymer and solvent

mixture which correlates with adsorption charac-
I I I I I

Xm.3 =x1,341 +x2.342 - xl.24142 (6)
Values of x,,? vary in a similar manner for the
three solvent mixtures and only slowly with the
solvent mixture composition (Fig. 5). Values of x ~
manifest higher dependence on the solvent mixture.
~ zms3versus +1 are well
When the curves of x , , and
separated (see Fig. 5A), h , values are lowest (i.e. in
NB/CH/PNVC system). When and x,,~ curves
are close (Fig. 5B),6, has slightly higher values (i.e. in
NB/D/PNVC), and finally when both curves inter-
sect (Fig. 5C), b , reaches the greatest values (i.e. in
NB/THF/PNVC).
These findings can be correlated with the a'
parameter from the Mark-Houwink-Sakurada
equation for binary systems (PNVC/solvent). As a'
increases in the order cyclohexanone < dioxane <
tetrahydrofuran, their respective mixtures with
nitrobenzene (which has the highest value of a'
TABLE 2. Values of the interaction parameters x , , ~and x ~for
three solvent-l/solvent-2 mixtures a t 298 K
9, (%I
Fig. 5. Interaction parameter, j(1.2r for solvent-l/solvent-2
mixtures, and ternary interaction parameter, x,,,~, for
PNVC/solvent-l/solvent-2 mixtures, versus volume fraction
, ~ nitrobenzene, d l : (a) 0 x1.2 for NB/CH; z,,,~. for
of
PNVC/NB/CH. (b) 0 for NB/D; 0 x , , ~for
, PNVC/NB/D.
(c) 0 j(1,2 for NB/THF; x,,,), for PNVC/NB/THF.
among these solvents) show rising values of and
also of h,. x ~ does , ~not reflect the effect strongly
because although x , , increases,
~ x1,3and x ~(eqn , 6)
~
balance, so that x ~ does, not
~ vary remarkably. For
instance, PNVC in T H F has a' = 0.65, which is close
to a' = 0 7 2 corresponding to PNVC in NB (Table 1).
So, PNVC with NB/THF mixtures should show a
greater number of adsorbed molecules of solvent-1,
or solvent-2, according to the mixture composition,
as has been noted. On the other hand, PNVC in
CH has the lowest a' value (Table 1 ) and so the
, PNVC
~ in the

4," NB/D NB/THF NB/CH

x1.2 xm.3 x1.2 Xm,s X1.2 Xm.3

~

20 0.239 0,436 0.352 0.410 0.1 29 0.455

40 0.345 0.396 0.502 0,352 0.194 0.431
60 0.333 0.405 0.480 0.369 0.195 0.432
80 0.214 0.458 0,306 0,436 0.130 0.459

a In VOI. % nitrobenzene.

BRITISH POLYMER JOURNAL VOL. 22, NO. 3.1990

Prejerential udsorption in polymerlsofvent-l/solvent-2 solutions
NB/CH/PNVC mixtures manifest the smallest
adsorption changes and also the lowest x1,2values
(Fig. 5A).
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