Investigation of Solution Rheology of LDPE and MMA

Graft Copolymer
Authors: Dilawar Azeem Rasool, Tahir Waheed, Muzammil Hanif, Sharjeel Ahmad
Supervisor: Ms.Nida Qamar
Department of Polymer and Process Engineering
University Of Engineering and Technology Lahore
Abstract
Effect of grafting Methyl methacrylate (MMA) on the rheological properties of linear low
density polyethylene (LDPE) solutions was to study. Grafting was done using melt mixing
through peroxide-initiated free radical polymerization. Rheological measurements were taken
using Brookfield DVIII+ Rotational Rheometer. Solution and Grafting for LDPE was
unsuccessful so shifted to polystyrene. Different solutions of Polystyrene (PS) in Xylene were
prepared and their rheological measurements were taken. Carreau model was used to fit the
results from rheometer and relaxation time was calculated. Then specific viscosity and intrinsic
viscosity was also calculated for different concentrations. Concentration dependence of
relaxation time and specific viscosity was studied and De Gennes scaling law for solutions was
used to find that solvent behavior was either as -solvent or good solvent.
Keywords: Solution Rheology, Polystyrene, Relaxation time, -solvent, Interaction

1. Introduction
Now days, modifications of non-polar polymers i.e. Polyolefin by grafting polar monomers is
under attention. Grafting can be used to improve adhesion, clarity, environmental stress cracking
resistance, thermo-oxidative stability, etc. Graft copolymers are potential additives to impart
improved compatibilizing influence in polymer blends.
[7]
They contain functional (polar) groups
with desirable polyolefin properties and act as effective interfacial agents to improve
compatibility with other materials.
[9]

The rheological behavior of polymers either solution or melts is very important in processing
and fabrication of polymers in order to make useful products. The shear flow of polymer
solutions both dilute and concentrated, employing either organic solvents or water, is
encountered in a wide variety of applications. Common examples include the addition of (2 % -
3 %) of a polymer such as poly methyl methacrylate (PMMA) to a mineral oil in order to
formulate multi grade motor; here the polymer serves to reduce the dependence of oil viscosity
on temperature and also to lower the pour point. More concentrated solutions, up to 30 % to 40
% polymer, are used to manufacture textile fibers by the process of solution spinning. Paints and



coatings are other applications of polymer solutions. In petroleum industry, dilute polymer
solutions are used for enhanced oil recovery.
[13]

LDPE is non polar and has strong intermolecular forces due to which it is inert in nature and
shows resistance to most of the chemicals. However incorporation of small amount of other
polymers can improve its interaction with solvents. Goal of grafting was to improve its
solubility, dye ability for better use in fiber production. Also LDPE/MMA could be used as a
compatiblizer for polar-nonpolar polymer systems.
In past years, many have worked upon grafting polar groups onto LDPE such as ethyl acrylate;
butyl acrylate etc.
[7]
Gamma irradiation method has been used to for grafting.
[14]
MMA has been
grafted onto Polyethylene-Polypropylene copolymer.
[9]
In our work, we used MMA and grafting
through peroxide-initiated free radical grafting.
Rheological study can be a useful tool to investigate solution properties. It gives you viscosity
changes in response to applied shear rate. Rheological model can be used to fit the data and data
obtained from it can be used to find relaxation time, specific viscosity and intrinsic viscosity.
Their results can give you an idea about the solvent behavior and either solvent thermodynamics
have been improved or not.
Carreau model was used to express the rheological data. Further scaling law was used to explain
the concentration dependence of specific viscosity and relaxation time. Rise in intrinsic viscosity
for different concentrations shows improvements in solvent interactions.

2. Experimentation
2.1. Materials
LDPE and polystyrene (injection grade)
Xylene (1.162kg/l) and toluene (1.1494kg/l) from Riedel-de Haen
MMA (general purpose grade)
BPO (industrial grade)
2.2. Grafting
Grafting of LDPE and MMA was carried out on a melt mixer.
Processing temperature 170C
Motor speed 50 rpm.
Composition: MMA 5% , Benzoyl peroxide (BPO) initiator 0.460%
Time 10 min
[7,1]

In order to check if theres been any grafting, differential scanning calorimeter (DSC)
was used to do thermal analysis and see if theres any change in melting point. First DSC
results of virgin LDPE were obtained and then of grafted LDPE. If we compare the DSC
results of virgin LDPE with that of LDPE-MMA graft polymer, it is clear that grafting is



Figure 2: DSC result of LDPE-MMA graft copolymer with 5% MMA, 0.460% BPO

not successful.(Figure 1,2) There is no significant change in the melting temperature of
the grafted polymer.
Main problem is that MMA has a boiling point of 100C and processing temperature is
170C. MMA evaporated even before polymer starts to melt. Hence LDPE-MMA grafted
polymer through melt mixing was not successful.
However, solution polymerization is a good option.
[9]






















Figure 1: DSC Result of virgin LDPE polymer



2.3. Solution Preparation
In order to prepare solutions of LDPE two solvents (xylene, toluene) were chosen.
[2,4]
First
solvent used was toluene. At room temperature polymer was left for a week to allow
dissolution at room temperature. After 1 week only a fractional amount was dissolved. So
temperature has to be elevated. For high temperature solution preparation high boiling point
solvent xylene was used. Within 25-30 min LDPE was dissolved in xylene at 80C. But as
the solution reached the room temperature gel formation occurred and LDPE precipitated.
(Figure 3a, 3b)


Other approach was to heat the solution for 5-6 hours to get a
stable solution at room temperature.
[3]
Condenser was also
used to compensate the solvent evaporation (Figure 3c). After
6 hours, solution was cooled down to room temperature and
same problem occurred.







Figure 3a
Figure 3b
Figure 3c


0
5
10
15
20
25
30
35
40
90 130 170 210 250
V
I
S
C
O
S
I
T
Y
(
C
P
)

RPM
Rheological Study of 1%
LDPE sol. in Xylene

However, rheological reading of LDPE at elevated temperature was carried out on
Brookfield DVIII+ rheometer.

(Table 1) shows all the readings taken using the rheometer. (Figure 4) shows the plot
between viscosity and rmp. It is clear from the graph that viscosity decreases as rmp is
increased. LDPE shows pseudoplastic behavior.
Hence, LDPE solution at room temperature was not possible. So we SWITCHED
Instead of LDPE, Polystyrene was used as it has many solvents and a stable solution was
possible at room temperature. Solvent used for PS was xylene.
2.4. Rheological Measurements
Rheological measurements were carried out using Brookfield DVIII+ LV model Rotational
Rheometer. Different solutions were prepared using different concentrations of PS using hot
plate apparatus at 80C for 30 min
Spindle LV1
Spindle speed 190-250 rpm 5 step size.
Temperature around 15C (room temperature)




Figure 4: plot of viscosity vs RPM for LDPE solution using
xylene as solvent. RPM is on x-axis
Table 1


8
9
10
11
12
13
14
15
16
17
18
19
20
38 58 78 98
V
i
s
c
o
s
i
t
y
(
c
p
)

Shear Rate s
-1

Viscosity-Concentration
Trend
4%
6%


3. Results and Discussions
3.1. Viscosity measurements
Polystyrene shows thickening behavior. Rise in shear rate gives rise in viscosity as structure
starts to build up but after reaching a critical shear rate, viscosity drops down. This is not due
to chain breakage but rather due to inertial effects.
[5,6]
inertial effects come from many
sources. One source is from instrument which is extra stress produced by the motor to
overcome its inertia and spindle inertia. This is normally corrected and calibrated by the
instrument provider.
[11]
Other reason is that even when water is being stirred it displaces from its rotation axis due to
its inertia and same behavior is followed by polymer solutions. However when using
rotational rheometer, we assume that flow is steady and one dimensional but at high speed,
secondary flows generate and flow may become nonhomogeneous, shear banding occurs and
regions of different shear rates are formed which as a result gives error in readings.
[12]
Concentration Dependency of Rheological Behavior
Two concentrations (4% and 6%)
Room temperature around 15C
Shear rate (41.8 to 101.8 s
-1
)



Shear thickening behavior of the solution was enhanced as concentration increased. (Figure
5) Higher values of viscosity were obtained at higher conc. (Table 2).


Table 2
Figure 5: plot of viscosity vs shear rate for two different concentrations:
4% and 6%


12
13
14
15
16
17
18
19
20
12 17 22 27 32 37 42 47
V
i
s
c
o
s
i
t
y
(
c
p
)

Temperature C

Viscosity-Temperature Trend
2
4
6
8
10
12
14
16
18
20
0 1 2 3 4 5 6 7
V
i
s
c
o
s
i
t
y

(
c
p
)

Concentration %
Viscosity-Concentration Relation
Table 3

Temperature Dependence of Viscosity
Viscosity readings were carried out at 45-18C with 0.05C error
Constant shear rate 78.8s
-1

6%. PS-Xylene





Concentration Dependence of Viscosity
Constant shear rate 86.8s
-1

Room temperature.











Figure 6: plot of viscosity at different temperatures
Table 4
Figure 7: plot of viscosity at different concentrations of PS in the solution


0
2
4
6
8
10
12
14
16
18
20
38 58 78 98
V
i
s
c
o
s
i
t
y
(
c
p
)

Shear Rate s
-1

Viscosity-Shear rate
6%
4%
2%
1.50%
1%
0.83%
0.63%
0.43%
0.23%

Modeling
Viscosities of other concentration solutions were also measured:

Carreau model was used to fit the data. Using this model relaxation time was measured for
different concentrations at different shear rates.


Specific viscosity
sp
was calculated using equation below:

Where is zero shear rate viscosity and
s
is solvent viscosity.
Intrinsic viscosity [] was calculated by plotting []/c versus c for each concentration where c is
the concentration. Increase in intrinsic viscosity shows improvement in polymer interaction with
the solvent.





Figure 8: plot viscosity vs shear rate at different concentrations of PS in xylene


0.00E+00
5.00E+05
1.00E+06
1.50E+06
2.00E+06
2.50E+06
3.00E+06
0 1 2 3 4 5 6 7
R
e
l
a
x
a
t
i
o
n

T
i
m
e
(
s
)

Concentration g/dL
Conc. dependence of relaxation time
0
2
4
6
8
10
12
14
16
18
0 1 2 3 4 5 6 7
S
p
e
c
i
f
i
c

V
i
s
c
o
s
i
t
y

(
c
p
)

Concentration g/dL
Conc. dependence of Specific Viscosity

Concentration Dependence of Relaxation Time








But scaling theory cannot be applied on it as these values could not be calculated accurately.
Concentration Dependence of Specific Viscosity









Looking closely to this graph, there should be three regions for the polymer:
Dilute Region
Semidilute Unentangled Region
Entangled Region
According to the scaling predictions specific viscosity
sp
of the neutral polymer in -solvent is
as C
2
in semidilute unentangled solutions and C
14/3
in entangled solutions, while the neutral
polymer in good solvent has
sp
~C
1.3
and
sp
~C
3.9
, respectively, in semidilute unentangled and
entangled solutions.
[10]

Figure 9: plot of relaxation time vs concentration for all the solutions
Figure 10: plot of specific viscosity vs concentration for all solutions



In our case, in semidilute unengtangled region fitting a linear line will give us 0.89 slope which
is deviated from 1.3 and slope of 1.56 in entangled region which is also deviated from 3.9 for
good solvents. These slopes were found by plotting natural log of both specific viscosity and
concentration.
[8]
4. Conclusion
Grafting of MMA on LDPE using melt mixing is not possible. LDPE cannot give a stable
solution at room temperature in any solvent. However at elevated temperature rheological study
shows that LDPE shows shear thinning behavior. Polystyrene can be easily dissolved in most of
the organic solvents and gives a stable solution at room temperature. It shows shear thickening
behavior. Its viscosity depends upon temperature and a rise in temperature will give fall in
viscosity. As we increase the concentration, viscosity curve shifts up. For a constant shear rate at
room temperature, at low concentrations up to 0.63 % rise in viscosity is linear but as we
increase the concentration change in viscosity is rapid. Main goal was to improve the solvent
thermodynamics by the incorporation of MMA in LDPE but this project was not successful.
However calculation exercise was done on PS. Results shows that in case of polystyrene-xylene
solution, it shows deviations from scaling theory and lies in between -solvent and good solvent
Acknowledgements
We are very thankful to Department of Polymer and Process Engineering. UET Lahore for
providing us materials and facilities for our project.

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