Eur. Polym. J. Vol. 28, No. 3, pp. 219-227, 1992 0014-3057/92 $5.00 + 0.

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Printed in Great Britain. All rights reserved Copyright © 1992 Pergamon Press plc

MOLECULAR STRUCTURE AND MELTING BEHAVIOUR

OF ETHYLENE-VINYL ACETATE COPOLYMERS
DANIELE C. BUGADA* and ALFREDRUDIN'~
Guelph-Waterloo Centre for Graduate Work in Chemistry, Department of Chemistry,
University of Waterloo, Waterloo, Ontario, Canada N2L 3GI

(Received 1 July 1991; in revisedform 13 August 1991)

Abstract--A series of ethylene-vinyl acetate copolymers has been examined by ~3C-NMR spectroscopy
and DSC. These polymers are products of high pressure free radical copolymerizations and contain 1~0%
vinyl acetate by weight. Such copolymers are random and almost all the vinyl acetate units are isolated
between ethylene units. All copolymers were branched, but total branching decreased with increasing vinyl
acetate content. This effect arises mainly because the vinyl acetate residues inhibit the formation of cyclic
intermediates that are involved in the productions of short branches. A decrease of about one short branch
per 1000 ethylene carbons is observed for every increase of 2 mol% vinyl acetate. About 10% of the vinyl
acetate units are branched at main chain carbons. Copolymers that have been cooled slowly from the melt
exhibit multiple melting peaks. The lower melting, minor peaks are believed to reflect crystallization of
lower molecular weight, branched molecules. The melting temperature of the copolymers is a function of
the average sequence length of crystallizable ethylene units, when allowance is made for vinyl acetate units
and short branches.

INTRODUCTION (c) The presence of the acetoxy functional

Ethylene-vinyl acetate copolymers are versatile
polymers which can vary significantly in their
chemical and physical properties. The numerous ap-
plications of these copolymers reflect the availability
of a complete range of comonomer compositions.
Ethylene-vinyl acetate copolymers (often referred to
as EVA copolymers) with about 1-40% by weight
vinyl acetate content are produced by a high pressure,
high temperature, bulk polymerization process simi-
lar to that employed for conventional high pressure,
free radical, low density polyethylene (LDPE). Some
of the distinctive features of EVA copolymers are as
follows.
(a) The ability of vinyl acetate and ethylene
monomers to copolymerize over a wide
range of compositions is a result of their
similar reactivity ratios. At higher tempera-
tures, where practical high pressure
reactions are performed, the reactivity ratios
are both close to 1.0 [1]. This condition
produces statistically random copolymers
with chemical compositions nearly identical
to those of the comonomer feeds.
(b) The major consequence of the incorporation
of the relatively bulky acetoxy side-group
into the polymer chains is a reduction in
polymer crystallinity. This feature is
especially true because of the random nature
of the copolymerization, which results in
most of the vinyl acetate residues being
incorporated as isolated units in the compo-
sition range mentioned above.
*Present address: Shell Canada Limited, P.O. Box 2100,
Oakville, Ontario, Canada L6J 5C7.
tTo whom all correspondence should be addressed.
group makes the copolymer more polar
than LDPE, EVA copolymers are also more
amenable to chemical modification such as
crosslinking or hydrolysis [2, 3].
(d) Free radical polymerizations of EVA
copolymers (like the analogous high press-
ure LDPE) produce branched products
containing both long and short branches,
These branches, which originate from
intermolecular [4,5] and intramolecular
[6, 7] H-atom abstractions, influence the
melt rheological and solid-state properties
of these polymers.
(e) Since the vinyl acetate monomer is a more
active free radical chain transfer agent than
ethylene, copolymer molecular weights are
limited to some extent by the amount of
vinyl acetate present in the feed.
In this work we have attempted a systematic study
of commercial, free radical polymerized EVA copoly-
mers with vinyl acetate contents ranging between l
and 40% by weight. We were mainly concerned with
the determination of the nature and extent of branch-
ing in these polymers and with branching variation as
a function of the vinyl acetate content, along with the
effects of both vinyl acetate units and branches on the
melting behaviour of the copolymers. This work is an
extension of previous studies of branching structures
present in high pressure LDPE [8, 9].
EVA copolymers have been studied extensively by
others. This work benefits from that of earlier
workers but the present data for short chain branch-
ing from ~3C-NMR analyses are believed to be more
accurate. Previous articles have often not been
concerned with quantitative measurements of branch
types and frequencies. In any event, lack of knowledge

219
220 DANIELE C. BUGADAand ALFREDRUDIN
of the optimum conditions for the acquisition of
~3C-NMR spectra would have confused the few
quantitative interpretations that may have been
attempted.
EXPERIMENTAL PROCEDURES
The EVA copolymers used for this study are all commer-
cial, free radical polymerized samples with vinyl acetate
contents ranging from 1 to 40%, by weight. The NMR
spectra of these samples were obtained with a Bruker
AM-250 spectrometer operating at 62.5 MHz with 10 mm.
o.d. tubes and sample concentrations in the 50-60 w/w% in
1,2,4-trichlorobenzene (TCB). The spectra were acquired
with no nuclear Overhauser effect, 35 sec relaxation time
and ca 2000 scans. These conditions have been shown to
give quantitative results in similar analyses of high pressure
LDPE [8].
Before inserting the sample tubes into the NMR spec-
trometer, the solutions were heated at 150°C for ca 30 min
(for samples with low vinyl acetate content) and 20 min (for
samples with high vinyl acetate contents). The polymers
were then examined at I00 °, in the NMR spectrometer. This
procedure has been shown to increase spectral resolution
and signal sensitivity of LDPE while simultaneously mini-
mizing sample degradation during data acquisition [8]. Peak
areas from the ~3C-NMR spectra were measured by
planimetry, which is believed to be more accurate than
digital integration.
All these EVA copolymers are commercial samples with
unknown thermal histories. A standard thermal pretreat-
ment was therefore adopted before differential scanning
calorimetric measurements were made. This pretreatment
was intended to establish a uniform thermal history for all
samples and to maximize the crystallinity with reasonable
expenditure of experimental time.
EVA specimens were compression moulded at 150°C into
discs, sandwiched between heavy AI foil (samples A-I) or
polyester foil (samples J-U) parting sheets. These foil-EVA
"sandwiches" were heated at 140°C for I hr and then cooled
to room temperature of 5°C/hr. This procedure has been
shown to produce compression moulded specimens with
controlled, reproducible thermal histories [I0, 11].
Specimens with 5.5mm dia and 9-11mgwt were then
stamped from these sheets and examined by differential
scanning calorimetry (DSC).
In the DSC instrument, the samples were heated in
crimped A1 pans at various heating rates, typically 2.5, 5.0,
7.5 and 10°C/min. The specimens were examined under a
static air atmosphere, over a 30-140°C temperature range
and with an empty, crimped A1 pan as reference. Instrument
calibration was obtained for thermograms of each sample
by use of a 7.6 mg indium standard, at a heating rate of
10°C/rain.
The melting temperature, Tm, defined as the temperature
at which total disappearance of crystallinity occurs [12], was
determined for each heating rate. Tm was measured as the
intersection of the baseline, following the transition, with
the tangent drawn to the steepest part of the transition, i.e.
at the higher temperature end of the transition. The Tm of
each sample was determined from a Tmvs heating rate plot
extrapolated to zero heating rate. The extrapolation was
obtained from a least square polynomial regression analysis.
RESULTS
General
There have been a number of N M R studies
reported on EVA copolymers [13-22]. These reports
include use of both ~H-[13, 14, 19, 20] and ~3C-NMR
spectroscopy [16-18, 20-22]. Most of these references
deal with monomer sequence distribution and
comonomer sequence length determinations
[13-15, 18-20] and configurational sequence lengths
[21]; use of shift reagents for spectral resolution
improvement [19, 21]; and solvent effects on
~H-NMR spectra [14, 15]. All are concerned with
chemical shift assignments of spectral lines. Most of
the literature quoted focusses on EVA copolymers of
high vinyl acetate content, as distinct from the
materials of this study.
In previous ~aC-NMR studies of EVA copolymers,
optimum experimental conditions for quantitative
analyses were generally not employed because of lack
of knowledge of the nuclear Overhauser enhancement
factor (NOEF) and the spin-lattice relaxation time
(Tt) for each carbon type in the copolymer. Although
these problems were recognized [16-18, 21 ], they were
avoided by using only chemically equivalent carbons
in any one set of calculations. This expedient could
not be employed in the present work since one of our
main objectives was to determine quantitatively
branching structures in EVA. This aim requires the
measurement of concentrations of different carbon
types. The problems mentioned were solved by
acquiring nuclear Overhauser suppressed t3C-NMR
spectra with a 35 sec delay time between successive
scans. We have shown [8], under similar conditions,
that 35 sec delay time satisfies the 5 x TI (max) of
LDPE molecules. This delay should therefore also
provide quantiative conditions for the hydrocarbon
portion of EVA copolymers, where most of the
branching occurs (as shown below). The work of
Grenier-Loustalot [22] provides quantitative spectral
band assignments.
Chemical shift assignments
Briefly, a typical IaC-NMR spectrum of an EVA
copolymer, obtained under the conditions detailed in
the experimental section, consists of a single peak at
169.23 + 0.06 ppm pertaining to the acetoxy carbonyl
carbon of the vinyl acetate unit. In addition there is
one peak at 74.22 + 0.04 ppm assigned to the methine
carbon of the vinyl acetate unit in a EVE comonomer
sequence distribution triad [16-18, 20, 21], where E
and V represent ethylene and vinyl acetate units,
respectively. At higher vinyl acetate contents (9% by
weight) other, smaller peaks appear slightly upfield.
These peaks can be assigned to both meso and
racemic EVV triads [16-18, 20, 21].
The most intricate region of the spectrum lies in the
0 - 4 0 p p m chemical shift range. Figures 1 and 2
illustrate distinct spectra for two samples having
significantly different vinyl acetate contents. Figure 1
is a partial 13C-NMR spectrum of sample C, contain-
ing 3.2wt% vinyl acetate. Its characteristics are
reminiscent of LDPE ~3C-NMR spectra reported
elsewhere [8]. Figure 2, on the other hand, is a partial
spectrum of sample R, which contains 30.7 wt% vinyl
acetate. It is evident that many of the peaks present
in Fig. 1 are smaller or absent in Fig. 2 whereas other
peaks originating from the vinyl acetate units are
more clearly present in the latter spectrum.
Table 1 lists the peak numbers (corresponding to
Figs 1 and 2), chemical shifts and peak assignments
for spectral lines in the 0 - 4 0 p p m range. These
spectral lines originate from both the hydrocarbon
 6
15

21

14

17 9 20
235

L, , = ...... I ~., . . . . . . . I ......... I .... , .... I ......... I

50 40 30 20 10 0
Fig. 1. Partial ~3C-NMR spectrum of sample C. Peak assignments are listed in Table 1.

11
/

14

20

15

19
21

L . . . . . . . ~ , J . . . . ¢ , . . . 1 . . . . . . . . . i . . . . . . . . . 1 . . . . . . . . . I
50 40 30 Z0 10 0
Fig. 3. Partial z3C-NMR spectrum of sample R. Peak assignments are llstcd in Table 1.
EPJ 28/3--B
222 DANIELi~ C. BUOADAand ALFRED RUDIN

Table 1. Chemical shifts of ~3Cresonance lines for EVA copolymers in 0-40 ppm range
Peak Chemicalshift Polymer
number in ppm~ Assignment component Spectral line description
1 39.36 _ 0.04 tiff EVA Backbone methylene carbon
2 38.03 + 0.02 brB4_. LDPE Methine branch point for butyl, amyl and LCB
3 37.11 + 0.07 brB2 LDPE Methine branch point for ethyl branches
4 35.25 + 0.02 fi~+ ~ EVA Backbone methylene carbon
5 34.62 __.0.03 fie EVA Backbone methylene carbon
6 34.43 + 0.02 ~tB4_. LDPE Backbone methylene carbon adjacent to butyl, amyl and LCB point
7 34.04 _+0.02 4B4 LDPE Methylene in butyl branch
8 32.67 + 0.01 3B5 LDPE Methylene in amyl branch
9 32.18 + 0.01 3B6_. LDPE Methylene in LCB
10 30.45 __.0.01 7B4_. LDPE Backbone methylene carbon thrice removed from branch point
11 29.99 Main backbone ---CH2 -
12 29.51 + 0.84 3B4 LDPE Methylene in butyl branch
13 27.23 -4-0.01 fiB4_ n LDPE Backbone methylene carbon twice removed from branch point
14 25.66 _+0.01 76 + EVA Backbone methylene carbon
15 25.54 + 0.18 76 EVA Backbone methylene carbon
16 23.93 + 0. l 1 ?
17 23.38 _+0.01 2B4 LDPE Methylene in butyl branch
18 22.89 + 0.01 2B6_ . LDPE Methylene in amyl and long branch
19 21.44 + 0.11 77 EVA Backbone methylene carbon
20 20.89 + 0.01 OAcMe EVA Methyl carbon of vinyl acetate group
21 14.17 _ 0.01 1B4_. LDPE Methyl carbon in butyl, amyl and LCB
22 11.19 + 0.23 IB2 LDPE Methyl carbon in ethyl branch at tertiary branch site
23 9.62 + 0.02 I B~~¢ LDPE Methyl carbon in ethyl branch at quarternary branch site
24 8.15 + 0.09 IB~b LDPE Methyl carbon in ethyl branch at quarternary branch site
*In TCB at 100°. Error in chemical shift is calculated with 95% level of certainty.
~'he prime and double prime superscripts tentatively imply different alkyl branches originating from a tetrafunctional branch site.
¢Speculative assignments.

(ethylene) c o m p o n e n t o f the copolymer [and thus are
designated using the n o m e n c l a t u r e scheme intro-
duced a n d a d o p t e d to L D P E [23] as well as the vinyl
acetate units (assigned by Greek letters as p r o p o s e d
by W u et al. [18])]. Peak assignments here are in
agreement with those m a d e by earlier workers cited
above.
Copolymer chemical composition and sequence length
determinations
T h e chemical compositions o f the E V A copolymers
u n d e r investigation were determined from ~3C-NMR
spectra using the vinyl acetate c a r b o n y l c a r b o n
resonance line are (Aco), the sum o f all spectrum
peak areas (AT) a n d the following equations:
Aco
y .... lO00 (1)
,48
1000 - 4y
x = - - (2)
2
Here x a n d y are the respective n u m b e r o f ethylene
a n d vinyl actate units per 1000 c a r b o n s in the copoly-
mer.
The weight percentage vinyl acetate (wac) is given
by:
86y
Wac = - - " 100 (3)
86y + 28
where 86 a n d 28 are the respective formula weights o f
vinyl acetate a n d ethylene.
As seen from Table 2, the vinyl acetate c o n t e n t o f
these copolymers ranges from 0.4 to 18.6mo1%.
These samples cover most o f the c o m p o s i t i o n range
characteristic o f E V A copolymers p r o d u c e d by high
pressure, high t e m p e r a t u r e free radical polymeriz-
ation processes.
N u m e r o u s previous reports have s h o w n t h a t the
m o n o m e r distribution in E V A copolymers is ideally
r a n d o m . T h a t is to say, these copolymers obey
Bernouilian statistics [13-18,20,25]. T h u s it is
possible to use the following equations to determine
the n u m b e r - a v e r a g e c o m o n o m e r sequence lengths o f
ethylene E a n d vinyl acetate ( V ) [12],
(E) = 1 + ~ (4)
Fv
( V ) = 1 + F~ (5)
Fo
where Fe a n d Fv are the mole fractions o f ethylene a n d
vinyl acetate, respectively.
F u r t h e r m o r e , it is possible to verify these
calculated sequence lengths from observed N M R
spectral line intensities. F o r instance, the observed
n u m b e r - a v e r a g e sequence length o f vinyl acetate
units, (V)obs, can be determined from vinyl acetate
methine c a r b o n resonance lines a n d the following
e q u a t i o n [25]:
EVE + VVE + VVV
(V)obs = E V E + I(VVE) (6)
where EVE, VVE a n d V V V represent triad peak areas
of ethylene/vinyl acetate/ethylene, acetate/acetate/
ethylene a n d acetate/acetate/acetate sequences,
respectively. Table 2 summarizes these calculated a n d
observed sequence lengths o b t a i n e d from the above
equations. G o o d agreement is f o u n d between ( V )
a n d Vobs, as expected. V, with a value close to unity,
does not vary significantly over the c o p o l y m e r com-
position range considered in this work. The average
vinyl acetate unit is isolated between ethylene residues
in E V A copolymers m a d e by high pressure processes.
The range of vinyl acetate sequence lengths is
narrowly distributed a r o u n d the m e a n value, for free
radical copolymerizations with the particular
c o m o n o m e r feed ratios t h a t are used to m a k e high
pressure E V A copolymers. Consider polymer U as a n
 Molecular structure and melting behaviour of EVA copolymers 223

Table 2. Comonomercompositionand sequencelengths for EVA copolymers

Number-averagesequencelengths
Weight % Mole% Mole % (E) (V) (V)
Sample VAc VAc(Fv) ethylene(Fe) [equation(4)] [equation(5)] obs.
A 1.2 0.4 99.6 250.0 1.00 1.00
B 1.3 0.4 99,6 250.0 1.00 1.00
C 3.2 1.1 98,9 90.9 1.01 1.00
D 6.7 2.3 97,7 42.5 1.02 1.00
E 7.2 2.5 97,5 40.0 1.03 1.00
F 7.3 2.5 97.5 40.0 1.03 1.00
G 7.9 23 97.3 37.0 1.03 1.00
H 8.4 2.9 97.1 34.5 1.03 1.00
I 9.4 3.3 96.7 30.3 1.03 1.07
J 15.2 5.5 94.5 17.2 1.06 1.04
K 16.2 5.9 94.1 16.9 1.06 1.06
L 16.7 6.1 93.9 16.4 1.07 1.05
M 18.7 7.0 93.0 14.3 1.08 1.05
N 21.6 8.2 91.8 12.2 1.09 1.06
O 24.5 9.6 90.4 10.4 1.11 1.09
P 25.6 10.1 89.9 9.9 1.11 1.10
Q 27.2 10.8 89.2 9.3 1.12 1.15
R 30.7 12.6 87.4 7.9 1.14 1.16
S 38.9 17.2 82.8 5.8 1.21 1.16
T 39.7 17.7 82.3 5.6 1.22 1.20
U 41.3 18.6 81.4 5.4 1.23 1.18

example. This material, with 18.6 mol% vinyl acetate,
is the copolymer richest in this comomomer. The
fraction of all V (vinyl acetate) sequences that contain
exactly nj units is given by:
N(V, nj)= [E]+r 2 [E.__]+r2 . (7)
W] iv]
Here r2 is unity, and [E] and IV] are the respective
molar concentrations of ethylene and vinyl acetate in
the comonomer feed. In this type of copolymerization
(where r I = r 2 = 1) [E] = F e and [V] = Fv. It can be
estimated then that 81% of the vinyl acetate sequences
are single units, only 15% are diads, 3% contain three
vinyl acetate units and tetrad runs comprise only 1%
of the vinyl acetate sequences.
This calculation assumes that the particular
copolymerization fits the simple Mayo-Lewis co-
polymer scheme, with unit reactivity ratios [1]. As
mentioned, the weight of evidence supports this
assumption. Any examination of the effects of vinyl
acetate incorporation on the physical properties of
EVA copolymers can thus reasonably treat the vinyl
acetate units essentially as isolated, single units.
Branching results
Ethylene-vinyl acetate free radical copolymeriza-
tions produce branched products. Chain transfer
reactions result in the formation of both long and
short chain branches, much as in the formation of
LDPE. In many cases, the branching in a polymer can
be detected and quantified by N M R area measure-
ments of "unique" resonance lines characteristic of
specific branch types. The intensities of these spectral
lines are directly proportional to branch concen-
trations when the N M R spectra have been acquired
under proper experimental conditions [24],
Some of these unique spectral lines may be found
in the ~3C-NMR spectra of both LDPE and EVA
copolymers, indicating the presence of similar branch
types in both polymers. These unique spectral lines
include peaks 8, 9, 17 (from Table 1) which are
characteristic of amyl, long and butyl branches,
respectively [22, 25]. (Note that present-day nC-NMR
counts C6 and longer branches as long.) Also, peaks
22 and 24 correspond to ethyl branches originating
from trifunctional or tetrafunctional branch points,
respectively. It should be stressed also that these
branching structures refer exclusively to the hydro-
carbon (ethylene) component of the copolymer.
Table 3 summarizes the types and concentrations of
the branches present in these copolymers. We note
that, in general, these EVA copolymers contain lower
branch concentrations than high pressure LDPE
[8, 9]. This point is especially noticeable at higher vinyl
acetate contents. Such an observation is not unex-
pected of course, since the branching structures men-
tioned originate from the ethylene components of the
copolymer, and thus branching should decrease along
with the mole fraction of the ethylene in the macro-
molecules.
We can, however, make a relative comparison of
ethylene-component branching concentrations in
EVA copolymers, regardless of the vinyl acetate
content, by converting branch concentrations from
branches per 1000 (ethylene + vinyl acetate) carbons
to branches per 1000 ethylene carbons. Furthermore,
by considering only the short chain branches (SCB),
one can observe the effect of the vinyl acetate units
on the intramolecular back-biting reactions respon-
sible for the formation of SCBs [6, 7].
Figure 3 summarizes these calculations. It shows a
plot of total SCB concentration per 1000 ethylene
carbons vs mole per cent vinyl acetate content. There
is a clear decrease in SCB concentration with increas-
ing vinyl acetate content. A linear regression analysis
on the points in Fig. 3 results in a coefficient of corre-
lation of 0.86. The scattering in these data may well
originate from different polymerization conditions
(such as different temperatures, pressures and types of
stirring) used by various manufacturers in the pro-
duction of these commercial samples. Figure 3 has a
negative slope of 0.55 which can be interpreted as an
approximate decrease of one SCB per 1000 ethylene
carbons for every increase of 2 mol% vinyl acetate.
224 DANmLE C. BUGADA and ALFREDRumN

Table 3. Vinyl acetate contents and branching characteristics of ethyle-vinyl acetate copolymers
Mole% vinyl Branches per 1000 carbons Acetate
acetate units
Sample contenP Long A m y l B u t y l Ethyl (3°) b Ethyl(40)c Total AcH/AcH
A 0.4 2.7 1.3 5.5 3.8 1.2 14.5 --
B 0.4 2.1 1.2 6.7 2.9 1.3 14.2 0.7
C 1.I 2.3 1.5 7.7 3.0 1.2 15.7 0.9
D 2.3 2.3 1.6 5.2 2.2 0 11.3 0.9
E 2.5 1.5 1.0 5.0 2.0 1.3 10.8 1.0
F 2.5 1.9 1.3 7.4 3.6 1.5 15.7 0.9
G 2.7 2.1 2.2 6.4 2.1 0 12.8 0.9
H 2.9 1.8 1.2 5.8 2.4 1.5 12.7 0.9
I 3.3 1.3 0.7 5.1 ~0.7 0 7.8 1.0
J 5.5 1.3 1.4 4.2 1.5 m0.8 9.2 1.0
K 5.9 1.8 1.2 3.8 1.5 ~0.7 9.0 0.9
L 6.1 1.2 1.0 4.0 1.6 ~0.8 8.6 1.0
M 7.0 1.5 1.1 3.9 1.3 ~0.7 8.5 0.9
N 8.2 1.7 1.6 5.6 d d 8.9 1.0
O 9.6 1.0 ~0.9 3.2 2.2 1.9 9.2 0.9
P 10.1 m0.7 0 2.5 1.2 0 4.4 1.0
Q I0.8 ~0.4 ~0.3 1.8 0 0 2.5 0.8
R 12.6 ~0.8 ~0.8 2.8 0 0 4.4 1.0
S 17.2 1.4 0 1.3 ~0.9 0 3.6 0.9
T 17.7 I.I ~0.3 1.6 0 0 3.0 0.9
U 18.6 0 0 2.0 0 1.5 3.5 0.9
'Determinedfrom the carbonyl carbon of acetate unit.
bEthyl branches at trifunctional branch sites.
CEthyl branches at tetrafunctional branch sites.
dDetected but not measurable.

These observations are consistent with expec- amount of methine H - a t o m abstraction will be
tations that the steric requirements o f the vinyl reflected in a decrease of the methine carbon
acetate group restrict the formation of cyclic six or resonance area as compared to the carbonyl carbon
s e v e n membered ring intermediates which are the resonance area, which should not vary.
p r e c u r s o r s for the intramolecular H - a t o m abstrac- We have thus used the ratio of methine to carbonyl
tions necessary for SCB formation [6, 7]. carbon resonance areas, i.e. Acu/Aco, as an
To this point, we have concentrated only on indication of the extent of chain transfer (branching)
branching structures which occur on ethylene at vinyl acetate units. A non-branched vinyl acetate
sequences in the EVA copolymers. It is also possible, unit should have a AcH/Aco ratio of unity, whereas
however, for branching to occur at vinyl acetate an increasing amount of branching will produce a
units. H - a t o m abstractions may occur particularly at decreased AcH/Aco ratio. Table 3 lists the Ac./Aco
methine carbons because they are more easily ratios for the polymers under investigation. It is clear
removed in free radical reactions than, say, methylene that H - a t o m abstractions result in branch formation.
carbons. Since each vinyl acetate unit contains one The length of these branches cannot be deduced but
methine and one carbonyl carbon, an increased it seems probable that they are long, on the assump-
tion that the vinyl acetate unit will hinder short chain
branch formation by back-biting mechanisms.
16 The data in Table 3 show that some branching may
(/I occur at vinyl acetate quaternary backbone carbon
Z
atoms. Approximately 10% of the vinyl acetate units
o ° in the copolymers of this study are branched. There
is no trend visible between branch frequency and vinyl
12
W acetate content. This result is hardly surprising, since
Z 8 these polymers are commercial products produced
>-
"I-
I¢ under a variety of unknown reaction conditions.
8 o
0 Thermal studies
~o o
i8 o
As indicated in the Experimental Procedures, the
EVA copolymers were subjected to a thermal
¢ 6
pretreatment prior to examination by DSC, so as to
establish comparable thermal histories for all the
0 0 0
o=4 samples. With one exception (sample T), all DSC
.J thermograms contain a major first order phase
~z o °o
transition pertaining to the melting temperature
o transition. The copolymers containing low vinyl
I i I i I i I i I acetate contents (i.e. samples A - I ) also show
00 4 8 IZ 16 ZO additional, smaller, endothermic peaks prior to the
MOLE I°/o) VAc CONTENT main transition. This "multiple melting phenom-
Fig. 3. Plot of total SCBs per 1000 ethylene carbons vs e n o n " has been observed for other polymers, includ-
tool% vinyl acetate content. ing polyethylene [26, 27].
 Molecular structure and melting behaviour of EVA copolymers
There have been several proposed explanations for
the multiple melting phenomenon. One is partial
melting, recrystallization and remelting [26-28] of
crystallites as the temperature in the DSC cell is
increased. Other explanations include molecular
weight fractionation during annealing and crystalliza-
tion [26], differences in crystal perfections [29] and
crystal lattice structure [30], or crystallite molecular
arrangement [31].
Figure 4 illustrates the multiple melting phenom-
enon for sample E. Recall that this, like other
samples, was cooled from the melt to room tempera-
ture at 5°C/hr. The top trace (curve A) represents the
original thermogram obtained from scanning the
temperature range 30-140°C. At 140°C, the sample
was then annealed for 10rain in the DSC cell
followed by quench-cooling at 45°C/min. The bottom
trace (curve B) represents the second heating of the
sample. It shows the absence of the multiple melting
phenomenon. Both curves A and B were obtained
with a heating rate of 5°C/min.
The minor peak observed on the first melting of
slow-cooled samples probably indicates the existence
of less stable crystailites that are formed during the
cooling process at temperatures lower than those of
which the major amount of crystallization occurs.
This effect is consistent with the crystallization of
segments of the polymer chains in which the main
chain length between vinyl acetate units, branch
points or chain ends is shorter than in less highly
branched molecules. High pressure, free radical
copolymerizations of ethylene are non-isothermal
reactions and the more highly branched species are
produced in the hotter reaction zones, where lower
molecular weight species are made. The species giving
the minor melting peaks that can be observed after
slow cooling are then probably the smaller, more
branched macromolecules. The second melting ther-
mogram of Fig. 4 does not reveal such minor peaks
because the polymers in this case have been cooled
from the melt at rates too great to permit any
A depression of a copolymer is related, to parameter P.
kO
| f f I f i
0 PO 40 60 80 I00 120
TEMPERATURE (*C)
Fig. 4. Influence of thermal history on melting endotherms
of sample E. Sample weight 10.7rag and heating rate
5°C/min for both traces.
225
significant crystallization of the species postulated as
responsible for the minor peaks that were observed
initially.
Melting temperatures obtained from DSC results
were analyzed according to Flory's theory of copoly-
mer crystallization [12, 32]. This theory relates the
equilibrium melting temperature (Tm) of a copolymer
to the equilibrium melting temperature of the pure
homopolymer (T °) of the crystallizable monomer
unit, in this case ethylene. According to this theory:
1 1 R
Tm T° AHu In(P). (8)
Here the melting temperatures of the copolymer and
the homopolymer of crystallizable units are Tm and
T °, respectively, AHu is the heat of fusion per
crystallizable repeating unit, R is the gas constant and
P is the probability that a crystallizable monomer
residue selected at random will be succeded by
another such unit.
Flory's theory assumes that longer sequences of
crystallizable monomer units form more stable
crystallites than shorter sequences and will thus melt
at higher temperatures. The theory relates the
equilibrium melting temperature of the copolymer to
the sequence distribution of crystallizable units rather
than just to the copolymer composition. This general
prediction is assessed in Fig. 5 where melting
temperatures from DSC measurements (Table 4) are
plotted against number-average ethylene sequence
lengths.
Curve A is a plot of ( E ) (from N M R analyses,
Table 2) against Tin. This plot implicitly treats all
ethylene units as crystallizable. Curve A is seen to
consist of two portions, with Tm rising steeply with
increasing (E), at ( E ) < 30 monomer units. These
particular copolymers have vinyl acetate contents
between about 19 and 5 mol% and have relatively
low branch contents, as summarized in Table 3. At
lower vinyl acetate contents, the melting temperature
rises more slowly with increasing ethylene sequence
lengths. The peculiar nature of this plot is a result of
the neglect of the effects of branching, however, as
shown below.
According to equation (8), the melting point
For a random copolymer (such as EVA copolymers),
P is equal to the mole fraction of crystallizable units
[32], i.e. P = Fe. It should be emphasized, however,
that EVA copolymers contain both vinyl acetate units
and branches that also decrease the sequence
probability, P. Therefore, vinyl acetate units and also
amyl, butyl and ethyl branches (collectively referred
to as co-units or defects) will also contribute to a
melting point depression of the copolymer. Long
chain branches are not considered to be part of the
co-unit content because segments of such branches
that are remote from the branch point may be
capable of co-crystallizing.
Table 4 summarizes the total mole% co-unit
content obtained by summing the mole% vinyl
140
acetate and short chain branch contents. It also
includes the corrected sequence probabilities, P, and
ethylene mole fractions, Ft. The differences between
P and F, are a result of the short chain branches
present in the polymer. (Note that branching at vinyl
226 DANIELEC. BUGADAand ALFREDRUDIN

I I I I I t I I I I I 1 I
0 20 40 60 80 100 ” 25C

(0 OR (D,
Fig. 5. Experimentally observed melting temperatures (7’,) from DSC as a function of number-average
ethylene sequence lengths, (E), as determined from copolymer composition ((E) = 1+ Fe/F,, open
circles, curve A) and copolymer composition plus short chain branching ((E)p = 1 + P/(1 - P). closed
circles, curve B).

acetate units, indicated by the AC-/A,, ratio in Table Although both plots in Fig. 6 are linear and have
2, was not considered as part of the co-unit content similar slopes, there is a significant divergence
because these branches orginate from a vinyl acetate between them, reflecting the differences between Td
unit which is already a defect. Further, the length of and T,.
branches at the vinyl acetate unit is not known.) The The quantitative shortcomings of equation (8) are
plot of the T,,, vs values of P that take account of well known and are suggested as connected at least in
branching is shown as curve B of Fig. 5. The exper- part with the difficulty of attaining equilibrium melt-
imental points form a common relation which seems ing temperatures experimentally [32]. Also, it seems
more reasonable than that estimated for curve A, on unlikely that an entire sequence of ethylene units
the basis of comonomer content. could be incorporated into a crystallite, because the
Equation (8) and the appropriate P values from hindrances imposed by vinyl acetate units or branch
Table 4 can be used to calculate the hypothetical points will extend past the immediate vicinity of such
melting temperatures (Tcalc) for the copolymers; defects. The linear form of equation (8) appears to be
results are summarized in Table 4. It is obvious that functionally correct for this range of copolymers,
for all samples T,,,, > T,,,, as illustrated in Fig. 6 however, and the data of Fig. 6 could be used to
which is a plot of T, and Tcalcvs P. define operational values of T”, and AHu for predic-
tion of melting temperatures of EVA copolymers
Table 4. Ethylene seqwnce probabilities, calculated melting tem- after the specific thermal treatment described in the
peratures and experimental T,,,s for EVA copolymers Experimental section.
Total
co-unit
Sample F, P x 100 mole% r,,. (c”) r, f 0.5 (“Cl
A 99.6 91.2 2.8 135.4 115.8
99.6 91.1 2.9 135.0 114.5
98.9 96.2 3.8 131.7 111.0
D 91.1 95.8 4.2 130.6 106.3
E 91.5 95.6 4.4 129.8 104.5
: 91.3
91.5 95.0
94.6 5.0
5.4 127.8
126.2 100.4
101.3

H 91.1 94.8 5.2 126.9 105.8

I 96.7 95.3 4.1 128.9 98.8
J 94.5 92.8 1.2 120.0 96.9
K 94.1 92.5 7.5 119.1 95.4
L 93.9 92.2 7.8 118.1 94.7
M 93.0 90.8 9.2 113.2 93.8
N 91.8 90.1 9.9 110.9 92.8
0 90.4 88.6 11.4 105.9 84.8
89.9 88.8 11.2 106.7 80.9
89.2 88.6 11.4 106.1 82.9
R 81.4 86.5 13.5 99.0 82.4
S 82.8 82.2 17.8 85.2 65.9
80 95 90 95 lO0

T 82.3 81.8 18.2 83.9 - P

U 81.4 80.4 19.6 19.5 62.9 Fig. 6. Experimentally determined melting temperatures
‘Calculated from equation (7) with AH,, = 970 cal/mol and (I-,,,) and calculated melting temperatures (Tuk) as functions
Pm= 418.5”K [30]. of ethylene sequence probability, P.
 Molecular structure and melting behaviour of EVA copolymers
Acknowledgment--Tiffs research was supported by the
Natural Sciences and Engineering Research Council of
Canada.
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