REGULAR CONTRIBUTED ARTICLES

M. Barmar*, M. Barikani
Department of Polyurethane, Fibers and Nanopolymers, Iran Polymer and Petrochemical Institute, Tehran, Iran

Investigation of the Thickening Efficiency of HEUR

on the Behavior of Two Different Latex Types

direct addition of a monoisocyanate to poly (ethylene glycol)

A hydrophobically modified ethoxylated urethane (HEUR) as a (PEG) or by addition of a large excess diisocyanate to PEG fol-
International Polymer Processing downloaded from www.hanser-elibrary.com by University of Minnesota on July 6, 2018

thickener was synthesized using poly (ethylene glycol), Dicy- lowed by addition of an alkyl amine to terminate the isocyanate
clohexylmethane diisocyanate (H12MDI) and cethyl alcohol groups. S-G HEURs with broad molecular weights are pro-
via step growth polymerization technique. The molecular duced by step growth process. These materials are prepared
weight of the thickener was determined by GPC, and its behav- by the reaction of a hydroxyl-end-capped PEG with a diisocya-
ior in aqueous solution was studied. The steady shear experi- nate to form isocyanate terminated prepolymer. The synthesis
ments were carried out by mixture of the synthesized thickener is followed by the reaction of isocyanate terminated prepoly-
with two resins. These resins had different nature; one with hy- mer with hydrophobic alcohols or amines (Barmar, 2001). A
drophilic and the other with both hydrophilic and hydrophobic schematic structure of S-G HEUR is shown in Fig. 1.
segmental structure. The result showed the type of resin can be Over the past few years, several major rheological studies of
effective in the thickening efficiency of HEUR thickener. HEURs in aqueous solution have been reported (May et al.,
1996; Dai et al., 2001a; Lundberg and Glass, 1991; Tam et al.,
1998; Tirtaatmadja et al., 1997; Vorobyova et al., 2001; Win-
nik and Yekta, 1997). The research in this area was carried
For personal use only.

1 Introduction out in various fields, e. g. the effect of molecular weight distri-

bution on rheology of HEUR aqueous solution, modeling of
Several key trends are driving the usage of low and zero VOC their viscoelastic behavior, interaction of HEUR with ionic
(volatile organic compound) based paints and coatings. These and nonionic surfactants in aqueous solution etc. (Alami et al.,
include stricter environmental regulation, the green building 1996; Dai et al., 2001b; Kaczmarski et al., 1999; Kaffashi
movement and increasing consumer awareness of the possible et al., 2005). Some research was also carried out on behavior
health risks associated with exposure to toxins emitted from of resins and associative thickeners. The rheological behavior
paints and coatings. of butyl acrylate/styrene/acrylic acid latices thickened with a
One of the solutions to the VOC problem is changing the HEUR thickener was investigated by Quadrat and his cowork-
solvent base systems to waterborne or aqueous systems. Unfor- ers (2003). Kostansek (2006) studied the colloidal interactions
tunately, waterborne systems, unlike the solvent base variety of both HEUR and HASE (Hydrophobically modified Alkali-
require a thickener to yield a viscosity that hold the paint ingre- Soluble) associative polymers with pigments to clarify the con-
dients in a homogeneous state and also contribute to its rheo- ditions needed to achieve good pigment dispersion in associa-
logical properties (Calbo, 1989). Many of the important appli- tive thickener systems.
cations, appearances, and resistance properties of a latex paint In our previous work, the influence of prepolymer molecular
depend on its appropriate viscosity at various shear rates and weight on viscoelastic properties of aqueous HEUR solutions
its encounters from manufacture to end use (Rokowski et al., was examined in a series of S-G HEUR thickeners (Barmar
1988). So, thickeners are one class of chemical additives that et al., 2004). The analytical grade of materials was used for
play a key role in the development of high performance coat- synthesis and preparation of those thickener models. In this re-
ings as rheology modifier (Chen et al., 1997). search, a S-G HEUR model was prepared using industrial
Hydrophobically modified ethoxylated urethanes (HEUR) grade of PEG, and the viscoelastic properties of aqueous
are as a well-known class of associative thickeners. HEUR HEUR solution were studied. The novelty of this work is to
thickeners are non-ionic materials and so they are not sensitive study the effect of two different lattices with various hydrophil-
to pH of the resins. These materials are divided in two main ic and hydrophobic segments on thickening efficiency of pre-
groups of Uni-HEUR and S-G HEUR, according to their meth- pared urethane thickener. The thickener model was synthe-
ods of preparation and molecular weight distribution. Uni- sized via preparation of prepolymers by the step-growth
HEURs with narrow molecular weights are synthesized by

* Mail address: Mohammad Barmar, Department of Polyurethane,

Fibers and Nanopolymers, Iran Polymer and Petrochemical Insti-
tute, P.O. Box 14965-115, Tehran, Iran
E-mail: m.barmar@ippi.ac.ir Fig. 1. Structure of S-G HEUR

218
Carl Hanser Verlag, Munich Intern. Polymer Processing XXIV (2009) 3
 M. Barmar, M. Barikani: Thickening Efficiency of HEUR on Two Different Latex Types

polymerization of poly (ethylene glycol) with a proper amount Physica rheometer model MCR 300 (Austria), using a cone-
of dicyclohexylmethane diisocyanate (H12MDI), with average and-plate fixture with 50 mm diameter, 28 angle cone. The dis-
molecular weight in the range of 6000 to 8000. Then, the tance of gap was 0.53 mm. All rheology measurements have
synthesized prepolymers were fully end-capped with excess been performed at 293 K. For the steady shear experiments,
dodecyl alcohol. Steady shear flow measurements were carried an equilibration time of 10 s was given at each shear rate to
on aqueous solution of thickener and mixture of thickener and allow the system to reach steady state.
lattices.
3 Results and Discussion
2 Experimental
The FTIR spectrum of the prepolymer is presented in Fig. 2.
2.1 Materials and Methods The presence of NCO groups in the structure of the prepolymer
at 2270 cm – 1 and also, polyurethane characteristic bands in
Industrial grade PEG 6000 (Mn = 4600 – 6000) was obtained the regions of 1720 cm – 1 (carbonyl groups in urethane) and
from Kimiagaran Emrooz company, Iran. Toluene, tetrahydro- 3330 cm – 1 (NH stretching) confirming the preparation of pre-
furan (THF) and dodecyl alcohol were purchased from Merck, polymer. The completion of the reaction and formation of final
International Polymer Processing downloaded from www.hanser-elibrary.com by University of Minnesota on July 6, 2018

Germany. Dicyclohexylmethane diisocyanate (H12MDI) with polymer is shown in Fig. 3. In the final product the absorption
trade name of Desmodur W was purchased from Bayer, Ger- band at 2270 cm – 1 related to unreacted NCO groups disap-
many and used as received. The details of the synthesis proce- peared.
dure were described in our previous work (Barmar et al., The number average molecular weight and polydispersity
2001). The molar ratio of OH/NCO was chosen as 0.478 and index (PDI) of synthesized thickener models are 8980 and
adjusted by weighting the proper amounts of the reactants. 1.94 respectively. The molar ratio of OH/NCO was adjusted
Two industrial grade lattices of non-plasticized aqueous dis- by weighting the proper amounts of the reactants. The data of
persion based on vinyl acetate (Veova) and acrylic acid esters, molecular weight was obtained by gel permeation chromato-
(Polyfam 420) and non-plasticized aqueous dispersion based graphy (GPC), using a Gynkotek pump, a Phenogel M 5 lm
on styrene and acrylic acid ester (Polyfam 735) from Resinfam column with 60 cm length and an ERC 7512 (EKMA) refract-
company, Iran, were studied. Surfactant type and concentration ometer. Chloroform was the mobile phase with a flow rate of
in the two lattices are the same. The specifications of these lat- 1.0 ml/min. A calibration curve was prepared with Polyethy-
tices are given in Table 1. lene glycols (Polymer Labs) standards.
For personal use only.

Infrared spectra were recorded on a Bruker-IFS 48 Fourier

transform infrared spectrophotometer (Bruker, Germany). The 100.9961
rheological properties of HEUR thickener in aqueous solution %
alone and its mixture with two lattices were measured by Paar 76.5399
Transmittance

52.0836
Parameters Standard method Polyfam 420 Polyfam 735
27.6274
Solid content (%) ISO 1625 50 ± 1 50 ± 1
Viscosity (cP) ISO 2555 8000 ± 4000 3500 ± 1500
PH-value ISO 976 4.5 ± 1 8 ± 0.5 3.1712
Minimum film ISO 2115 –1 15
forming (8C)
Density (g/cm3) ISO 2811 1.05 1.02 4000 3000 2000 1500 1000 cm-1 500
Hardness, Koenig (s) ISO 1522 6 17 Wavenumber
Fig. 3. Completion of the reaction and formation of final polymer
Table 1. Specification of Polyfam 420 and 735

103
101.3095 4 % conc.
Pa s 3 % conc.
%
2.5 % conc.
94.3207 102
2 % conc.
3330 cm-1 1.5 % conc.
Viscosity
Transmittance

87.3319 2270 cm-1

101

1720 cm-1
80.3431
100
73.3543

10-1 -3
10 10-2 10-1 100 101 s-1 102
4000 3000 2000 1500 1000 cm-1 500 Shear rate
Wavenumber
Fig. 4. Steady shear viscosity profiles as a function of shear rate for
Fig. 2. FTIR spectrum of the prepolymer aqueous solutions with various concentration of HEUR

Intern. Polymer Processing XXIV (2009) 3 219

 M. Barmar, M. Barikani: Thickening Efficiency of HEUR on Two Different Latex Types

The steady shear viscosity profiles as a function of shear rate The relation between viscosity and shear rate of Polyfam
for aqueous solutions with various concentrations of HEUR 420 samples are also given in Fig. 5. The viscosity behavior
model are illustrated in Fig. 4. In general, there are three stages of Polyfam 735 against shear rate is shown in Fig. 6. This resin
in the curves. The first stage, at low shear rates, is Newtonian has also low viscosity and this viscosity is reduced with slightly
viscosity, where viscosity is not dependent on the shear rate. increasing shear rate.
In the third stage, the viscosity is reduced significantly at high For proper mixing of this thickener with resins, the model
shear rates. This is due to disruption of the association network thickener was dissolved in 75 cm3 double distilled water first
at high shear rate. The association network is a physical net- and then was added to 100 cm3 resin. The amount of thickener
work and can be destroyed in high shear rate fields. In spite of was 2, 3, and 4 g, so by addition to 75 cm3 water and 100 cm3
these two stages, there is another stage where viscosity is in- of resin, the weight percentage of thickener will be 1.15, 1.71
creased at increasing shear rate. This behavior is called shear and 2.28 %. These data are given in Table 2.
thickening and also was reported by other researchers (Kacz- The behavior of samples prepared with Polyfam 420 and dif-
marski et al., 1999; Sharon and Stuart, 2001; Svanholm et al., ferent amount of thickener is given in Fig. 7. As it can be seen,
1997). This behavior is due to changing of chain orientation by introducing urethane thickener in these resins, the viscosity
between associated thickener micelles to bridges between is increased at both low and high shear rates. For example, the
viscosity of pure resin at shear rate of 0.1 s – 1 for Polyfam 420
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micelles. The associated network is reinforced by these

changes and the viscosity is slightly increased (shear thicken- is lower than 1 Pa · s (Fig. 5). But for the sample of 420-04,
ing). The rearrangement of network is being restricted due to that have 2.28 % of thickener, the viscosity at shear rate of
increasing of thickener concentration and viscosity, which re- 0.1 s – 1 is above 200 Pa · s. It has also been found that, the vis-
duces the chain mobility. So the phenomenon of shear thick- cosity of pure resin no. 420 at shear rate of 10 s – 1 is 0.1 Pa · s,
ening is reduced by changing concentration from 1.5 to 4 %. but for the sample of 420-04 is about 30 Pa · s at shear rate of
Also, the shear thinning profiles of high viscose aqueous so- 10 s – 1, and 20 Pa · s at shear rate of 1000 s – 1.
lutions (3 and 4 %) were affected by this parameter. How- The viscosity profile versus shear rate for samples of Poly-
ever, by continuous increasing of shear rates, the network fam 735 with different weight percent of thickener are also giv-
structure is destroyed, and the viscosity is reduced (shear en in Fig. 8. As the Polyfam 735 resin has two different nature;
thinning). hydrophicity and hydrophobicity, by addition of thickener, the
For personal use only.

101 103
Polyfam 420-04
Pa s Pa s Polyfam 420-03
Polyfam 420-02
102
Viscosity

Viscosity

100

101

10-1 100 -2
10-2 10-1 100 s-1 101 10 10-1 100 101 s-1 102
Shear rate Shear rate
Fig. 5. Relation between viscosity and shear rate of Polyfam 420 sam- Fig. 7. Relation between viscosity and shear rate of samples prepared
ples with Polyfam 420 and different amount of thickener

10-1 103
Polyfam 735-04
Pa s Pa s Polyfam 735-03
Polyfam 735-02
102
Viscosity

Viscosity

10-2

101

10-3 100 -3
10-2 10-1 s-1 100 10 10-2 10-1 100 101 s-1 102
Shear rate Shear rate
Fig. 6. Relation between viscosity and shear rate of Polyfam 735 sam- Fig. 8. Relation between viscosity and shear rate of samples prepared
ples with Polyfam 735 and different amount of thickener

220 Intern. Polymer Processing XXIV (2009) 3

 M. Barmar, M. Barikani: Thickening Efficiency of HEUR on Two Different Latex Types

Sample Polyfam 420 Polyfam 735 Thickener DD Water* Weight percent

g g g cm3 %

420-02 105 (100 cm3) – 2 75 1.15

420 – 03 105 (100 cm3) – 3 75 1.71
420 – 04 105 (100 cm3) – 4 75 2.28
735 – 02 – 105 (100 cm3) 2 75 1.15
735 – 03 – 105 (100 cm3) 3 75 1.71
735 – 04 – 105 (100 cm3) 4 75 2.28

* double distilled water

Table 2. Recipe for mixing of resin with thickener

higher viscosity is built up in comparison with Polyfam 420. In hydrophilic segments, improve associated networking in appli-
another way, in the low shear rate viscosity region in mixture cation of HEUR, and this is the reason of improving thickening
International Polymer Processing downloaded from www.hanser-elibrary.com by University of Minnesota on July 6, 2018

of Polyfam 735 and thickener, by increasing amount of thick- efficiency of HEUR model in Polyfam 735 resin.
ener, the viscosity is slightly decreased. This behavior may As mentioned before the type of resin has an important role
lead to inhomogenity in the mixture. It means some of the on thickening efficiency of HEUR thickeners. Overall, the
thickeners stay beside of the associated network. This behavior low shear viscosity of HEUR model and Polyfam 735 mixture
may be the reason for the difference in viscosity profile at low- is more than the HEUR model and Polyfam 420 mixture. But
er shear rate around 0.1 s – 1. By increasing shear rate to an the viscosity-shear rate curve slope of Polyfam 420 is more
amount higher than 0.1 s – 1, the system leads to better homoge- than of Polyfam 735. This phenomenon is related to hydrophil-
neity and the behavior of the samples become normal. So the ic- hydrophobic structure of Polyfam 735. Although, the Poly-
samples with higher amount of thickener, show higher viscos- fam 735 structure gives higher low shear viscosity, by increas-
ity. ing HEUR model concentration (2.28 %), the dispersion of
Usually, for the study of thickener efficiency, the variations HEUR model in Polyfam 735 was weaker. Hence at the point
of viscosities are compared at low shear rate with consideration of 2.28 wt.% of the thickener, the efficiency of the HEUR
of thickener percentages. The thickening efficiency of model model in both resins was similar.
For personal use only.

thickener in Polyfam 420 and Polyfam 735 resins are shown

in Fig. 9. As it is shown in this figure, from 0 to 1.71 wt.% of
thickener model concentration, the slope of the curve for low
shear viscosity of the resin mixture with thickener versus the 4 Conclusion
weight percent of thickener is considerable. The HEUR thick-
eners have a known structure of a hydrophilic backbone with In this study, a polyurethane thickener model was synthesized
two hydrophobic end segments. The thickening behavior of and used. This hydrophobically modified ethoxylated urethane
these materials is also due to this structure. By introducing was prepared via step growth polymerization of poly (ethylene
these chemicals to aqueous media, the hydrophobic segments glycol), H12MDI and cethyl alcohol. The thickener model
are centered and hydrophilic parts are distributed in water, showed reasonable thickening efficiency in aqueous media.
and due to this effect the flower like micelles are prepared. The performance of HEUR thickener was investigated in two
Some part of these thickener chains are acted as a bridge be- different resins. The steady shear viscosity measurements
tween two neighboring micelles (Xu et al., 1996). The results showed that thickening efficiency of polyurethane thickener
of this effect is a three dimensional network with thickening model in the resin containing both hydrophobic and hydrophil-
behavior. The Polyfam 735 resin with both hydrophobic and ic segment (Polyfam 735) is more than that of hydrophilic resin
(Polyfam 420). This was attributed to the similarity in chemical
structures of Polyfam 735 and HEUR thickeners which im-
400
proves the associating network and in turn the thickening effi-
Polyfam 420
Pa s ciency.
Polyfam 735
300

250
Viscosity

200
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Intern. Polymer Processing XXIV (2009) 3 221

 M. Barmar, M. Barikani: Thickening Efficiency of HEUR on Two Different Latex Types

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222 Intern. Polymer Processing XXIV (2009) 3