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 Copyright © 2014 American Scientific Publishers Journal of
All rights reserved Colloid Science and Biotechnology
Printed in the United States of America Vol. 3, 351–354, 2014

Temperature Effect on the Intrinsic Viscosity of Aqueous

Poly(N-vinylcaprolactam) Solution
Moez Guettari1
∗ , Lilia Ajroudi1 , Tahar Tajouri1 , Ahmad Bitar2 , and Abdelhamid Elaissari2
1
Unité de Recherche, RMN Dans Les Polymères Et Les Composites, Institut Préparatoire Aux études D’ingénieurs de Tunis,
1089 Montfleury, Tunisie
2
University of Lyon, F-69622, Lyon, France, University Lyon-1, Villeurbanne, CNRS, UMR 5007, LAGEP-CPE;
43 bd 11 Novembre 1918, F-69622 Villeurbanne, France

Poly(N-vinylcaprolactam) is prepared via batch radical precipitation polymerization of

N-vinylcaprolactam monomerusing cationic radical initiator. The viscosity of diluted polymer
was examined versus of temperature ranging from 25  C to 40  C. The intrinsic viscosity and
the polymer-solvent interactions were determined and examined on the basis of the Huggins’s
equation. The Huggins constant was found to be positive below 32  C which is the Lower Critical
Solution Temperature (LCST) for this homopolymer. However, in the LCST range, the sign of the
Huggins constant changes due to the turbidity of the medium induced by polymer precipitation.
The intrinsic viscosity and Huggins constant variation versus temperature prove the associative
nature of the prepared end-charged poly(N-vinylcaprolactam).
Keywords: Poly(N-vinylcaprolactam), Intrinsic Viscosity, Temperature.

1. INTRODUCTION
Stimuli-responsive polymers show a sharp change in prop-
erties upon small or modest change in environmental con-
dition, e.g., temperature, light, salt concentration, electric
and magnetic fields, electromagnetic radiation, mechanical
stress or pH


. The nature of the response can be chemi-
cal, mechanical, electrical, optical, phase separation, shape
change


.
Temperature-sensitive polymers are the most commonly
studied class of stimuli-responsive polymeric systems;
these polymers are composed by a hydrophobic and/or a
hydrophilic part. The critical temperature solution is the
temperature at which the phase of polymer and solution is
discontinuously changed according to their composition.1
If the polymer solution has one phase below a specific,
it has a lower critical solution temperature (LCST). Oth-
erwise, it is called an upper critical solution temperature
(UCST).
The polymers of LCST are used as model in the field
of drug delivery. Several synthetic polymers such as
poly(N -isopropylacrylamide),2 poly(N ,N _-diethylacryl-
amide),3 poly(N -(l)-1-hydroxymethyl-propylmethacryl-
amide),4 poly(N -acryloyl-N -alkylpiperazine),5 poly
(N -vinylcaprolactam)6 are prepared, studied and reported
∗
Author to whom correspondence should be addressed.
RESEARCH ARTICLE
in the literature as evidenced by the numerous published
works.7
Regarding poly(N -vinylcaprolactam) homopolymer it
was first synthesized in the 1950s8 and only few works
were reported in the literature.9 10 Over the last two
decades, the poly(N -vinylcaprolactam) has attract specific
attention mainly in drug delivery.11–15 PNVCL is a non-
ionic, biodegradable, water-soluble, non-adhesive polymer,
belonging to the same family of poly(vinylpyrrolidone).
Unlike poly(N -isopropylacrylamide), PNVCL is non-toxic
and stable against hydrolysis. Moreover, PNVCL is a valid
alternative to poly(N -isopropylacrylamide), and an inter-
esting candidate for biomedical and pharmaceutical appli-
cations, such as drug encapsulation for well control of
drug-delivery, as support of enzymes, and in some fine
applications such as biomolecules separation. Studying the
rheological properties of a thermo-responsive polymer can
be useful to determine its critical temperature and the
effect of temperature on the physical chemistry proper-
ties of its solution. The intrinsic viscosity is an interest-
ing quantity, which is interpreted as the volume occupied
by an isolated polymer chain and can be easily deduced
from capillary viscometer measurements. Then, the aim
of this study is to prepare the poly(N -vinylcaprolatam)
homopolymer solutions and to study their viscosity as a
function of temperature ranging from 25  C to 40  C.

J. Colloid Sci. Biotechnol. 2014, Vol. 3, No. 4 2164-9634/2014/3/351/004 doi:10.1166/jcsb.2014.1107 351

 Temperature Effect on the Intrinsic Viscosity of Aqueous Poly(N -vinylcaprolactam) Solution Guettari et al.

2. EXPERIMENTAL PART 0.35

2.1. Poly(N-vinylcaprolactam) Polymer Preparation 32°C

Poly(N -vinylcaprolactam) is prepared via batch radical 34°C
0.3 36°C
precipitation polymerization using 0.5 g of N -vinyl- 38°C
40°C
caprolactam and 0.1 g of cationic radical initiator (V50,
2,2 -Azobis (2 methylpropionamidine) di-hydrochloride). 0.25
The polymerization was conducted in ionized water during

ηrd (dl g–1)

6 h at 70  C.
0.2

2.2. Sample Preparation and Viscosity Measurements

The used concentrations of PNVCl, C0 = 0
8 g/dl, was 0.15
prepared and a series of polymer concentration, 0.4, 0.2,
0.1 and 0.025 g/dl, was obtained by successive dilution by
using deionized water. The viscosity measurements were 0.1
0 0.1 0.2 0.3 0.4 0.5
conducted with a semi automatic Visco Clock (Schott
Instruments) and an Ubbelohde glass capillary viscometer C (g dl–1)
(K = 0
003). The temperature of the studied samples was Fig. 2. The reduced viscosity versus polymer concentration in the 32  C
controlled (±0.01  C) by a thermostated bath type CT72/P. to 40  C.
The viscosity of a sample was determined by measuring
respectively the flow times t0 and t of the pure solvent polymer concentration depending on temperature are
and the solution for various concentrations. The viscome- detected. In fact, for the 25  C–31  C temperature range,
ter was thoroughly washed with distilled water and put in the curves slope are positive (Fig. 1), however for the
an oven after each experiment 32  C–40  C temperature the curves slope becomes neg-
ative (Fig. 2). The intrinsic viscosity [] is determined
according to the Huggins equation:16
3. RESULTS AND DISCUSSION
The reduced viscosity of the PNVCl aqueous solution is rd  + KH 2 C (2)
deduced from the flow times measurements of the pure
solvent, t0 , and the solution; t: Where, KH is the Huggins constant which measures the
RESEARCH ARTICLE

 polymer-solvent interaction constant. The KH value indi-

1 t cates the polymer behaviour. In fact, when 0
4 < KH < 0
5,
rd ≈ −1 (1)
C t0 the polymer-solvent interactions are attractive. However,
where, C is the polymer concentration. the polymer-solvent interactions are repulsive when 0
5 <
We report in Figures 1 and 2, the variation of the KH < 1. For high values of Huggins constant, KH > 1, the
reduced viscosity versus the PNVCl concentration. Two polymer chains aggregate.
distinct behaviours of the reduced viscosity versus the The effect of temperature on the intrinsic viscos-
ity and Huggins constant parameter are reported in
0.12
0.35
25°C
0.11 27°C
29°C
31°C 0.3
0.1

0.5
ηrd (dl g–1)

0.09
[η] (dl g–1)

0.08 0.2

0.07 0.15

0.06
0.1

0.05
0 0.1 0.2 0.3 0.4 0.5
0.05
C (g dl–1) 20 25 30 35 40 45
T (°C)
Fig. 1. The reduced viscosity versus polymer concentration in the 25  C
to 31  C. Fig. 3. The intrinsic viscosity versus temperature.

352 J. Colloid Sci. Biotechnol. 3, 351–354, 2014

Guettari et al. Temperature Effect on the Intrinsic Viscosity of Aqueous Poly(N -vinylcaprolactam) Solution

4 Table II. The molar self-association constant of PNVCl over the

25  C–31  C temperature range.

3 T ( C) 25 27 29 31

KM (dl/g) 0.0255 0.0200 0.0127 0.0034

2

This constant is connected to the intrinsic viscosity of the

KH 1
polymer according to Eq. (4).
0 KH 
KM = (4)
6
–1 The variation of the molar self-association constant versus
temperature is reported in Table II. This constant (KM )
–2 decreases with increasing temperature; this means that the
20 25 30 35 40 45
T (°C)
increasing of the volume occupied by a single chain is
due to a decreasing of the inter-chain cohesion and/or a
Fig. 4. The Huggins constant parameter versus temperature. dissociation of the clusters.
When the temperature exceeds the LCST, the Huggins
constant values become negative. Above this temperature,
Figures 3 and 4. The intrinsic viscosity and the con- the system is not considered as a polymer solution and
stant Huggins values are reported in Table I. The inver- the Huggins constant indicates that the polymer precipi-
sion of the Huggins constant sign is accompanied by a tates. The studied system is considered as a dispersion of
turbidity of the studied solution; this indicates that the particles in a continuous medium.
LCST is in the 31  C–32  C temperature range. The last According to Solomon et al.20 PNVCl has good solu-
result is in agreement with those reported by several bility in several organic solvents. One of the best solvents
authors.17 18 for poly-N -vinylcaprolactam is cold water 14  C–20  C.
In fact, when the temperature is lower than the LCST, In fact, at this temperature range, the solubility in water
the intrinsic viscosity increases while the Huggins constant of poly-N -vinylcaprolactam is a result of polar-group sol-
decreases with increasing temperature. This indicates that

the volume occupied by a single polymer chain increases
as a function of incubating temperature. This is due to
the disaggregation of the polymer chains. Then proving
not only the thermal sensitivity of the PNVCl but also its
associative effect.
According to the Cluster theory proposed by Pan et al.19
the reduced viscosity of an associative polymer solution
can be expressed by the following:
rd =  + 6KM C
RESEARCH ARTICLE
vation. In fact, in aqueous solution the polymer contains
an important number of water molecules bound to C O
groups by hydrogen bonds.
When the temperature increases, the self-association of
the polymer chain decreases, and so the volume occupied
by an isolated chain increases. These chains disaggregate,
and the intensity of the attractive intra-macromolecular
interaction decreases by increasing temperature. However,
when the temperature exceeds the LCST, a diminishing of
bound water molecules occurs, the solvation of the poly-
(3) mer diminishes leading to polymer precipitation.

where, KM is the molar self-association constant result-

ing from either inter-chain cohesion or cluster formation. 4. CONCLUSION
The reduced viscosity variation of poly(N -
vinylcaprolatam) aqueous solution versus polymer con-
Table I. The intrinsic viscosity and the Huggins constant parameter in centration present two distinct behaviours depending on
the 25  C–40  C temperature range. temperature. Then, the intrinsic viscosity, the constant
T ( C) [](dlg−1 ) KH interaction parameter, deduced according the Huggins
constant, and the inter/intra macromolecular interactions
25 0.0504 3
0393 of poly(N -vinylcaprolatam) in water were deduced over
27 0.0567 2
1165 the 25  C–40  C temperature range. In fact, for the 25  C–
29 0.0704 1
0811
31 0.0928 0
2194
31  C temperature range, the Huggins constant is positive,
32 0.1056 −0
1169 and becomes negative for the 32  C–40  C temperature
34 0.1396 −0
6320 range. The inversion of the Huggins constant sign is
36 0.1824 −0
9813 accompanied by a turbidity of the studied solution. The
38 0.3157 −1
4757 thermo-responsive character of this polymer is evidenced
40 0.2559 −1
2579
with an upper critical solution temperature above 32  C.

J. Colloid Sci. Biotechnol. 3, 351–354, 2014 353

 Temperature Effect on the Intrinsic Viscosity of Aqueous Poly(N -vinylcaprolactam) Solution
In fact, when the temperature is lower than 32  C, the
polymer chains aggregate and their volume increases
by increasing temperature. The molar self-association
constant resulting from either inter-chain cohesion and/or
cluster formation is calculated according to the cluster
theory. This constant increases by increasing temperature,
which means that the effect on the volume occupied by
a single chain is due to a decreasing of the inter chain
cohesion and/or a fragmentation of the formed clusters.
This indicates also the associative nature of polymer.
However, when the incubation temperature is above 32  C,
the polymer collapses and the solution becomes turbid.
So, the system can be considered as a dispersion of
self-assembly of PNVCL particles in a continuous water
medium.
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Received: 26 October 2014. Accepted: 14 February 2015.
J. Colloid Sci. Biotechnol. 3, 351–354, 2014