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A Novel Interpretation of Polymer Viscosity in Mixed

Solvents
a a a
Lilia Ajroudi , Moez Guettari & Tahar Tajouri
a
Unit de recherche RMN dans les polymres et dans les composites. Institut prparatoire
aux tudes d'ingnieurs de Tunis. Universit de Tunis. Tunisie
Accepted author version posted online: 11 Jun 2015.

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To cite this article: Lilia Ajroudi, Moez Guettari & Tahar Tajouri (2015): A Novel Interpretation of Polymer Viscosity in Mixed
Solvents, Journal of Macromolecular Science, Part B: Physics, DOI: 10.1080/00222348.2015.1051933

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 ACCEPTED MANUSCRIPT

A Novel Interpretation of Polymer Viscosity in Mixed Solvents

Lilia Ajroudi**, Moez Guettari* and Tahar Tajouri***

Unit de recherche RMN dans les polymres et dans les composites. Institut prparatoire aux

tudes dingnieurs de Tunis. Universit de Tunis. Tunisie

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*
Corresponding author E-mail: gtarimoez@Yahoo.fr

**
Corresponding author Lilia Ajroudi : lilia_ajroudi@yahoo.fr

***
Corresponding author Tahar Tajouri : tahar.tajouri@ipeit.rnu.tn

Running title:

Viscosity of polymers in mixed solvents

Keywords: Polymer viscosity, Grunberg-Nissan constant d, mixed solvents, intermolecular

interaction.

Abstract

A novel interpretation of the viscosity of a polymer in mixed solvents in the dilute concentration

regime is presented. The ternary system polymer/solvent 1/solvent 2 was considered as a quasi-

binary system and the presence of the polymer acts as a perturbation on the mixed solvents

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where the interaction between unlike molecules was quantified by the Grunberg-Nissan constant,

d ' . Thus, a pseudo-Grunberg-Nissan constant, d 'p , was introduced to quantify the interaction

between the unlike molecules of the mixed solvents in the presence of the polymer. The effect of

the polymer addition on the interaction between unlike molecules was quantified by introducing

the deviation of the Grunberg-Nissan constant, dd p' = d p - d , concept which is connected to

both the intrinsic polymer viscosity and the Huggins constant in pure and mixed solvents. This

novel interpretation of the viscosity data was used to study the effect of polystyrene dissolution
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on the interaction between benzene and ethyl acetate at 20C.

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INTRODUCTION

Conformational analyses [1-3] consist of the determination of the changes in a polymers

dimensional parameter, such as radius of gyration, hydrodynamic radius or intrinsic viscosity,

with a thermodynamic parameter variation or with molecular interactions such as polymer

polymer and/or polymer-solvent. The dimensional parameters can be determined by using

appropriate techniques [4], where radius of gyration and hydrodynamic radius are determined,

respectively, by static light scattering and dynamic light scattering, and intrinsic viscosity can be
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determined by viscosity measurements.

The capillary technique is a simple, inexpensive and very useful method for the

determination of a polymers intrinsic viscosity and the polymer-solvent

interaction. It consists in the measurements of the times of flow of the solvent and

the polymer solution in the dilute concentration regime. The specific viscosity and

the reduced viscosity can be deduced from the measured flow times for solvent and

various polymer concentrations in the dilute regime. Several equations have been

proposed to determine the polymer intrinsic viscosity and the polymer-solvent

interaction parameter, such as the Huggins-Kramer equations [5-6] and the Schulz-

Blaschke equation [7].

The behaviors of a polymer in mixed liquids have attracted the attention of a number of authors

[8-19]. Several conformations have been shown to be manifested depending on the polymer

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solubility and the physical properties of the mixed liquids. In fact, mixed liquids can be

completely or partially miscible with each other, and the liquids can be good, theta or poor

solvents for the polymer. Thus, a panoply of phenomena have been observed, including polymer

co-non-solvency in a mixture of its good solvents [17], and the polymer cosolvency in a mixture

of its non-solvents [18]. Castellanos et al. [19], for instance, have shown that polyethylene glycol

undergoes conformational changes near the critical point of an isobutyric acid- water mixture.

It has been well established that changes in the polymers conformations are due to the physical
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properties of the mixed liquids. Usually, the non-ideality of the mixture has been described by

the excess properties, such as enhanced viscosity, which are a macroscopic manifestation of the

interactions between unlike solvent-solvent molecules. The main question considered in this

paper is how a polymer affects the interactions between unlike molecules in mixed liquids. As

the structure of a mixed liquid is due to the interaction between their unlike molecules, the

discussion can be focused on the quantification of the effect of the polymers presence on the

interaction between unlike molecules in mixed solvents.

It has been proposed that the interactions between unlike molecules can be quantified from

viscosity measurements by calculating the Grunberg-Nissan constant d [20]. In the dilute

concentration range, where the interactions between polymer chains are weak, the ternary system

composed of a polymer and a mixture of two liquids can be considered as a quasi-binary system

of mixed liquids. Considering this hypothesis, we develop a theory to quantify the effect of the

polymer presence on the interaction between the unlike molecules in a mixed solvent from the

experimental data obtained from viscosity measurements. This resulted in our novel

interpretation of the viscosity of a polymer in mixed solvents. Finally, the obtained results will

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be examined to study the effect of polystyrene (PS) on the interaction between benzene and ethyl

acetate at 20C.

THEORETICAL BACKGROUND

Competing forces in the ternary system include excluded-volume interactions, van der Waals

interactions, and solvent-mediated hydrodynamic interactions. According to Grunberg-Nissan

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[20], the interaction between unlike molecules 1 and 2 can be quantified by calculating the

constant d at a mole fraction of the liquid 1, X1, according to the following equation:

ln h m - ( X 1 lnh1 + (1 - X 1 ) lnh 2 )
d' = (1)
X 1 (1 - X 1 )

where h1 , h 2 and h m are, respectively, the dynamic viscosities of liquids 1and 2 and the mixture.

By assuming that the presence of the polymer does not affect the composition of the binary

mixture liquid, we can define a pseudo Grunberg-Nissan constant, d p' , at a mole fraction X1 of

liquid 1 in the mixed liquid (independent of the polymer concentration). This parameter

quantifies the interactions between the unlike solvent molecules in the presence of the polymer:

ln h m* - ( X 1 lnh1* + (1 - X 1 ) ln h 2* )
d =
'
p
, (2)
X 1 (1 - X 1 )

where h m* , h 1* and h *2 are, respectively, the dynamic viscosities of the polymer in the solvent

mixture and in the individual liquids 1 and 2, at the same concentration of polymer. By

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combining equations (1) and (2), the deviation of the Grunberg-Nissan constant, dd ' , due to the

presence of polymer in the mixed liquids can be expressed by the following :

ln(Gi ) h m,r
dd ' = d p' - d ' = and Gi = , (3)
X1 (1 - X1 ) ( ) X1
h 1, r (h 2 ,r )1- X 1

where h m ,r , h1,r and h 2, r are, respectively, the relative viscosities of the polymer in mixture and

liquids 1 and 2, in the presence of the polymer. These quantities are taken at the same
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temperature and polymer concentration, C.

According to the Huggins equation [5], the reduced viscosity, h red , is connected to the polymer

concentration as follows :

h red = [h ] + K H [h ]2 C , C < C * (4)

1
h red = (h r - 1) , (5)
C

where, K H , C * , h r and [h ] are, respectively, the Huggins constant, the overlap concentration,

which separates the dilute from the semi-dilute concentration regimes, the relative viscosity and

the intrinsic viscosity. The Huggins constant is a measure of the interaction between polymer and

solvent.

In the dilute regime and by combining equations (4) and (5), the relative viscosity of a polymer

solution can be connected to its concentration, according to the Huggins equation:

h r = 1 + [h ]C + K H [h ]2 C 2 , (6)

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We denote by [h ]m , [h ]1 and [h ]2 the intrinsic viscosities of the polymer in the mixed solvents at

the molar fraction X1 and in pure solvents 1 and 2. K H , m , K H ,1 and K H , 2 are, respectively, the

Huggins constants of the polymer in the mixed solvent and solvents 1 and 2. Thus, the relative

viscosity of the polymer in mixed solvents and solvents 1 and 2 are given by the following

equations:

h m ,r = 1 + [h ]m C + K H ,m [h ]2m C 2 (7)
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h1,r = 1 + [h ]1 C + K H ,1 [h ]12 C 2 (8)

h 2, r = 1 + [h ]2 C + K H , 2 [h ]22 C 2 (9)

Taking into account equations (7), (8) and (9), the quantity Gi takes the following form:

1 + [h]m C + KH ,m [h]m C 2
2

Gi = (10)
(1+ [h] C + K
1 H ,1 [h] C
2
1
) (1+ [h] C + K
2 X1
2 H ,2 [h] C
2
2 )
2 1- X1

Thus, the effect of polymer dissolution in the dilute concentration regime in mixed solvents can

be quantified by equation (11):

1+ [h]m C + K H ,m [h]m C 2
2
dd ' =
1
( )( )
ln (11)
X1 (1 - X1 ) 1+ [h] C + K [h]2 C 2 1 1+ [h] C + K [h]2 C 2 1
X 1- X
1 H ,1 1 2 H ,2 2

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EFFECT OF POLYSTYRENE DISSOLUTION ON THE INTERACTION BETWEEN

BENZENE AND ETHYL ACETATE

Munk et al. [21] have determined the intrinsic viscosity of polystyrene, [h ]m , as a function of the

volume fraction of ethyl acetate, f2 , in the mixture of benzene, solvent 1, and ethyl acetate,

solvent 2, at 20C. The intrinsic viscosity excess [22-25] of polystyrene, [h ]E , in a benzene/ethyl

acetate mixture can be calculated according the following equations:

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[h ]E = [h ]m - [h ]i and [h ]i = f1 [h ]1 + (1 - f1 )[h ]2 (12)

The obtained results were plotted versus the benzene volume fraction, f1 , as shown in Fig. 1. A

small deviation from the ideal intrinsic viscosity, [h ]i , was observed for all of the benzene

volume fraction range at 20C with [h ] at f1 = 0.5 being 3.8 ml/g, for instance. In order to
E

quantify this deviation, we calculated its relative deviation, rd , to the ideal intrinsic viscosity by

the following equation :

100 [h ]
E

rd =
[h ]i (13)

As in Table 1, the maximum value of the relative deviation was about 8%. This is probably due

to the quasi- ideality of the benzene/ethyl acetate mixture. In fact, Munk et al. [21] estimated the

benzene/ethyl acetate interaction parameter, c12 , from activity coefficients measured at the

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boiling point under normal pressure by Chao and Hougen. [26].The studied mixture forms an

almost ideal solution with c12 ca. equal to 0.09.

The effect of polystyrene on the interaction between ethyl acetate and benzene mixture

molecules at 20C was studied. As the polymer concentrations were small, in g/ml: 0.004, 0.003,

0.002 and 0.001, the presence of the polymer in the mixed solvents can be considered as a

perturbation on the interaction between benzene and ethyl acetate. Thus, the quantity, Gi ,was
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first calculated according to equation (10) by using the polystyrene intrinsic viscosities and

Huggins constants data reported by Munk et al. [21] for the polymer concentration range at

20C. Then the deviation of the Grunberg-Nissan constant dd ' was calculated according to

equation (3) for the polymer concentration range and for different benzene molar, X1, fractions

according to equation (14):

1
X1 = , (14)
V 1 - f1
1 + 1m
V2 m f1

where f1 , V1m and V2m are, respectively, the benzene volume fraction, the molar volume of

benzene and the molar volume of ethyl acetate at 20C.

Figure 2 shows the deviation of the Grunberg-Nissan constant, dd ' , as a function of the benzene

molar fraction. When X1<0.5, a quasi-linear dependence was detected for the studied polystyrene

concentration range. However, the deviation of the Grunberg-Nissan constant became constant

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when the benzene molar fraction exceeded 0.5. These observations mean that the presence of

polymer in the mixed solvents can affect the mutual interactions between unlike molecules.

According to Munk et al. [21], the intrinsic viscosity of polystyrene increased when an infinite

quantity of benzene was mixed with ethyl acetate; this is supported by the positive values of the

intrinsic viscosity excess of polystyrene at X1=0.9. In fact, the dissolution process of a polymer

involves solvent diffusion and chain disentanglement. The chain conformation, which is

quantified by the intrinsic viscosity, is an equilibrium state governed by the interactions polymer-
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polymer and polymer-solvent. When a polymer is dissolved in mixed solvents, the chain

conformation is a result of the interactions polymer-polymer, solvent 1-polymer, solvent 2-

polymer and solvent 1-solvent 2. For small X1, the benzene can be viewed as a perturbation on

the polystyrene/ethyl acetate system. As the benzene is a better solvent than ethyl acetate, the

polystyrene tends to be solvated preferentially by benzene. In order to moderate this

perturbation, the ethyl acetate attracts the benzene molecule which explains the positive

deviation of the Grunberg-Nissan interaction parameter at small X1. As the quantity of benzene

increased, the deviation decreased, and became constant when the benzene molar fraction

exceeded 0.5; this indicated that the effect of the presence of polystyrene became independent of

the composition of the liquid mixtures.

Several experimental results and theoretical developments have shown that a polymer usually

presents a preferential affinity [27-33] to one solvent when it is dissolved in mixed solvents,

which indicates that the interaction between the solvents can be affected by this behavior. In our

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opinion the deviation of the Grunberg-Nissan constant can be connected to the preferential

adsorption [30] of one component of the binary liquid (benzene) by the polystyrene.

Figures 3 and 4 show the variation of dd ' versus the polystyrene concentration; a linear

dependence was observed for all molar fractions X1.

For very small polymer concentrations, C<<C*, the quantity ln( Gi ) can be approximated by

neglecting the high order terms in polymer concentration:

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ln Gi ([h ]m - ( X1 [h ]1 + (1 - X1 )[h ]2 ))C (15)

Then the dd ' depends on the mixture composition and the intrinsic viscosities of the polymer in

the solvents/mixture. By combining equations (3) and (15) the effect of the presence of a

polymer on the interaction between unlike molecules of its mixed solvents takes this form:

([h]m - ( X1[h]1 + (1 - X1 )[h]2 ))C

dd ' (16)
X1 (1 - X 1 )

The last equation supports the observed behaviours of the deviation of the Grunberg-Nissan

constant parameter versus the polymer concentration.

CONCLUSIONS

We have developed in this study a novel approach to interpret the viscosity data of a polymer in

a mixed solvent. This method permits studying the effect of polymer dissolution on the

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interaction between the unlike solvent molecules in mixed liquids when the polymer is in the

dilute concentration regime. The ternary system is considered as quasi-binary and the presence of

the polymer acts as a perturbation to the binary liquid mixture. In the presence of the polymer

and according to the quasi-binary system hypothesis, the interaction between unlike molecules is

quantified by a pseudo Grunberg-Nissan constant. An expression for the deviation of the

Grunberg-Nissan constant due to the presence of a polymer was theoretically established and

discussed. The present method was successfully used to discuss the effect of the polystyrene
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dissolution in the benzene/ ethyl acetate mixture. The present method can be extended to study

the effect of dissolution of impurities, ions or molecules, on the interaction between completely

or partially miscible liquids.

Funding

The authors gratefully acknowledge financial support from the Tunisian Ministry of Education,

Research and Technology.

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Table 1: The relative deviation of the intrinsic viscosity from its ideal values for the various

benzene volume fractions, at 20C.

f1 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

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rd 2.68 4.39 5.95 6.50 6.93 7.41 7.94 7.70 6.51

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[h ]E (ml/g) 2

-1
0 0,2 0,4 0,6 0,8 1
f1

Figure 1. Excess intrinsic viscosity of polystyrene in benzene/ethyl acetate mixtures,

[h ]E (ml/g), vs. benzene volume fraction, f1 , at 20C.

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0,18

0,16
C=0.004 g/ml
C=0.003 g/ml
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dd 0,14 C=0.002 g/ml

C=0.001 g/ml
0,12

0,1

0,08

0,06

0,04

0,02
0 0,2 0,4 0,6 0,8 1
X1
Figure 2. The Grunberg-Nissan deviation, dd , vs. benzene molar fraction, X1, for
various polystyrene concentrations at 20C.

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0,12

X1=0.10 9
0,1 X1=0.21 6
X1=0.30 2
X1=0.42

0,08
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dd 0,06

0,04

0,02

0
0,001 0,0015 0,002 0,0025 0,003 0,0035 0,004

C(g/ml)

Figure 3. The Grunberg-Nissan deviation parameters, dd , vs. polystyrene

concentrations at 20C for the 0.11 to 0.42 benzene molar fraction range.

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0,05

0,045
X1=0.54 2
X1=0.62 3
0,04 X1=0.70 2
X1=0.84 5
X1=0.90 8
0,035
Downloaded by [New York University] at 01:07 12 June 2015

dd
0,03

0,025

0,02

0,015

0,01
0,001 0,0015 0,002 0,0025 0,003 0,0035 0,004

C(g/ml)
Figure 4. The Grunberg- Nissan deviation parameters, dd , vs. polystyrene
concentration at 20C for the 0.54 to 0.91 benzene molar fraction range.

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