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ABSTRACT: The effect of methyl acrylate content in ethylenemethyl acrylateacrylic acid (EMAAA) terpolymers
and acrylic acid content in ethyleneacrylic acid (EAA)
copolymers was investigated in blends of these two materials. The EMAAA terpolymer with 8 mol % methyl acrylate
was not miscible with any EAA material no matter what
the AA content, whereas the terpolymer with only about 2
mol % methyl acrylate was miscible, at least to some extent,
with the EAA copolymer at high acrylic acid contents.
Evidence supporting this conclusion derived from gloss,
differential scanning calorimetry testing, and dynamic me-
INTRODUCTION
To develop new polymeric materials for both scientic
and commercial purposes, the blending of two or
more different polymers is often used. Industrially,
the blending process is almost always carried out in
the molten state. At equilibrium, the amorphous components of both polymers may exist as a single homogeneous phase that would, in turn, mean that the two
polymers are miscible; that is, the two materials are
compatible. In most cases, however, the amorphous
components of the two polymers will separate into
distinct phases consisting primarily of the individual
components. Further, if there exists sufciently long
uninterrupted blocks of one repeat unit on both copolymers, then the two blocks can cocrystallize. Cocrystallization has recently been the subject of investigations for ethylene copolymers made with metallocene
or ZieglerNatta catalysts.1 4 In this article, we were
primarily interested in blends of polyethylenes made
without the use of site-selective catalysts; studies of
Correspondence to: B. Grady (bpgrady@ou.edu).
Contract grant sponsor: Chulalongkorn University.
Contract grant sponsor: NSF CARRER; contract grant
number; DMR-9733068.
Journal of Applied Polymer Science, Vol. 91, 2216 2222 (2004)
2003 Wiley Periodicals, Inc.
Key words: blends; ethyleneacrylic acid copolymer; ethylenemethyl acrylateacrylic acid terpolymer; mechanical
properties; calorimetry
2217
TABLE I
Copolymer Compositionsa
Grade
Ethylene
Methyl
acrylate
Acrylic
acid
310
320
EAA1
EAA2
EAA4b
EAA5
0.950
0.893
0.988
0.974
0.974
0.961
0.023
0.070
0.027
0.028
0.012
0.026
0.026
0.039
2218
PONGRAKANANON ET AL.
Figure 3 Tan versus temperature for EAA/320 terpolymer blend compositions that have constancy of tan over a
wide temperature range near room temperature.
2219
Figure 4
Figure 5
2220
PONGRAKANANON ET AL.
the most part well described by the sum of the properties weighted by the fraction of each component.
One signicant exception to this is the tensile strength
for the EAA5 blend; there is a clear synergistic behavior at high copolymer contents. This synergistic behavior was not found for either the modulus or elongation, although the sample-to-sample variation in the
former means that even if such an effect were present,
it could not be identied. The hardness, shown in
Figure 10, also shows the same synergistic effect at
high EAA contents. However, the crystallinities are
not higher, as shown in Table II, so this data does not
support increased crystallinity as the cause of the synergistic effect, however these samples do have a different thermal history than samples tested mechanically.
The only sample that showed clear evidence of two
separate melting transitions in DSC experiments was
EAA1. Spectra for blends with EAA1 are shown in
Figure 11 along with a representative sample that
showed no clear evidence of two distinct crystallite
phases, sample EAA2. The results of melting temperature measurements are shown in Table II; however,
baseline determination was deemed to be too difcult
to obtain accurate crystallinity measurements from
these DSC curves. Hence, the fractional crystallinity
was determined by X-ray crystallography experiments, where the sample thermal history was chosen
to mimic that in DSC experiments. This statement also
highlights an important point: the thermal history of
samples in the DSC and XRD measurements was different from that for all other measurements; additional
thermal processing detailed in the experimental section was performed on the samples used for DSC and
XRD measurements.
Based on the location of the melting transitions, the
two crystalline populations in EAA1 are clearly terpolymer-rich and copolymer-rich, with the latter pre-
2221
TABLE II
Properties of Polyethylene Crystallites for 310 Blended with Various EAAs
EAA1
% EAA
0.0
20
40
50
60
70
80
90
100
Tm /(C)
86.3
89.3
89.2c
89.8c
101.1
EAA2
b
EAA4
Tm /(C)
% Crystallinity
Tm /(C)
% Crystallinity
Tm /()
% Crystallinityb
11.8
12.5
13.2
11.7
13.8
15.3
16.1
18.0
20.1
86.3
92.8
95.4
96.8
97.6
11.8
5.2
9.7
12.8
10.4
12.0
16.0
15.0
18.2
86.3
92.8
95.5
94.8
96.6
11.8
11.5
14.0
11.2
13.1
10.3
14.9
13.3
15.6
86.3
87.5
90.7
92.5
93.1
11.8
8.0
10.1
9.7
10.8
8.8
12.6
9.8
10.8
97.8
EAA5
% Crystallinity
98.1
97.2
97.2
93.7
94.6
These values represent the temperature where the maximum heat ow occurred and was calculated from DSC measurements. The error bars on these measurements are approximately 1C.
b
These values are from XRD measurements. The error bars on these measurements are approximately 2%.
c
In these samples, there were two crystalline peaks corresponding to a phase containing primarily 310 and a phase
containing primarily EAA. The melting temperatures corresponding to the latter were identical for all samples and were
101.1C within experimental error, as shown in Figure 11.
CONCLUSIONS
Blends of ethylenemethyl acrylateacrylic acid terpolymers and ethyleneacrylic acid copolymers form
apparently miscible blends if the terpolymer has sufciently low methyl acrylate content and the copolymer has sufciently high acrylic acid contents as evidenced by one glass-transition temperature and one
crystallization melting point. For the highest acrylic
acid content copolymer, there was a synergistic effect
in tensile strength and hardness attributed to the
higher crystallinity versus either pure component. Although the phenomenon of cocrystallization in LDPE
copolymers has not been investigated in detail, this
cocrystallization is perhaps the most interesting features of these blends.
2222
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