Polymer Tesring 16 (1997) 193-198

0 1997 Elsevier Science Ltd

PII: SO142-9418(96)00047-5 Printed in Great Britain. All rights reserved
0142-9418/97/$17.00
ELSEVIER

MATERIAL CHARACTERISATION

NMR Carbon-13 High Resolution Study of

Poly(ethylene-co-vinyl acetate)

Giovanni Chaves Stael & Maria I&s Bruno Tam-es*

CCTNENF, Av. Albert0 Lamego, 200, cep: 28015-620 Campos, RJ, Brazil

(Received 14 July 1996; accepted 20 August 1996)

ABSTRACT

The poly(ethylene-co-vinyl acetate), EVA has been analysed by j3C high-resolution

using nuclear magnetic resonance (NMR) employing solution and solid state tech-
niques. The analyses of this copolymer by solution NMR permitted the copolymer
composition to be obtained, and using solid-state NMR, a study of molecular mobility
was carried out. Both studies were made to correlate the structure and properties.
0 1997 Elsevier Science Ltd. All rights reserved.

1 INTRODUCTION

Poly(ethylene-co-vinyl acetate), EVA, has been widely used for utensil manu-
facture due to its mechanical properties. Its properties depend on vinyl acetate
content in the main chain, and also on the polymerization process. When the
percentage of vinyl acetate is in the range of O&5%, the polymerization pro-
cess is normally in bulk, the molecular weight is low and the crystallinity is
higher than that obtained by a solution process. It is known that the basic
properties are closely linked to the structure. Hence, a correlation between
structure-properties is a good way to get a better characterization of a poly-
mer. In this study, the nuclear magnetic resonance spectroscopy was used to
obtain further information on the EVA structure. A comparison between magic
angle spinning (MAS) and CPMAS spectra is able to show the presence of
different domains or microdomains in a sample.* The variable contact-time

*To whom correspondence should be addressed.

193
194 G. C. Stael. M. 1. B. Tavares

experiment permits us to observe distinct regions that have different

mobilities.3,7
The characterization of molecular motion and sample homogeneity can be
determined from relaxation data, particularly by proton spin-lattice relaxation
time in the rotating frame (TiHp) and spin-lattice relaxation time in the labora-
tory (T,H>.5-9 One purpose of this work was to characterize the EVA as a
matrix to mix with natural fibres obtained from sugar cane. NMR was used as
it allowed us to obtain-information on both chemical structure and molecular
mobility. However, the main purpose of this work was to fully investigate the
EVA copolymer using both solution and solid-state NMR techniques in order
to obtain as much information as possible to better understand the composites
that have been prepared.

2 EXPERIMENTAL

2.1 NMR measurements

The solution NMR spectra was obtained on a VARIAN Gemini 300 spec-
trometer operating at 300.1 MHz and 75.4 MHz for H and i3C, respectively.
All experiments were done at ambient probe temperature using a 90 pulse
angle and the NOE effect was eliminated. The concentrated solution was 20%
in 1,2,4 trichlorobenzene and deuterium benzene as a lock solvent.
All solid-state NMR spectra were obtained on a VARIAN VXR 300 spec-
trometer operating at 299.9 MHz and 75.4 MHz for H and 13C, respectively.
All experiments were done at ambient probe temperature and performed using
gated high power decoupling. A zirconium oxide rotor of 7 mm diameter with
Kel-F caps were used to acquire the NMR spectra at rates of 4.5 kHz. Carbon-
13 spectra are referred to the chemical shift of the methyl group carbons of
hexamethyl benzene (17.3 ppm). The i3C were carried out in the cross-polariz-
ation mode with magic-angle spinning (CPMAS); variation contact time
(VCT) and magic-angle spinning (MAS). A range of contact time was estab-
lished as 200-8000 p.s. Proton T,p were determined from the intensity attenu-
ation of Cl3 peaks with increasing contact time.

3 RESULTS AND DISCUSSION

A preliminary quantitative solution C I3 NMR spectrum showed that the EVA

has a great domain constituted by ethylene sequences (Fig. 1). The compo-
sition proportion of each monomer was calculated and 13% of vinyl acetate
 NMR 13C high resolution study of EVA 195

(170.1 35.47 ~26.5

~74.8 I (21.6
L-

160 140 120 100 80 60 40 20

wm

Fig. 1. Carbon- 13 NMR quantitative solution spectrum of EVA, 20% in 1,2,4 trichlorobenzene
and deuterium bezene as lock solvent.

was found in this copolymer, which was confirmed by thermal gravimetric

analysis.
Analysing the MAS spectrum (Fig. 2), observing only the flexible region,
the peaks were assigned as belonging to CHz from flexible ethylene sequences
and the others belonged to vinyl acetate. The glass transition temperature (T,),
observed by differential scanning calorimetry (DSC), is -23*3C, which is in
agreement with the acetate content. The resonance line located at 14.8 ppm
was assigned as methyl branched from the ethylene sequence, which was very
small in the solution spectra. The CPA4AS spectra showed only one wide
signal at 33.0 ppm (Fig. 3) that was assigned, as the CH, belonged to the
ethylene rigid sequence. The other peaks did not appear, due to the fact that
the contact time was not enough to detect all NMR signals. In this case, and
maybe for several other copolymers which are constituted by two monomers
that have different mobilities, just one technique at solid state cannot give as
much information as is needed. The variable contact-time experiment must
be recorded, because many responses can be made from it. In the EVA case,
two distinct domains were detected, one formed by ethylene rigid sequences,
located at short contact-times and the other one constituted by ethylene flexible
196 G. C. Stael. M. 1. B. Tavares

r30.7

180 160 140 120 100 80 60 20 40 0

wm

Fig. 2. Carbon-13 NMR MAS spectrumof EVA.

70 60 50 40 30 20 10 0
mm

Fig. 3. Carbon-13CPIMAS spectrumof EVA.

(31.2 ppm) and the vinyl acetate groups, concentrated at long contact-times
(Fig. 4). The spectra at short contact-times only present the signal detected
by the CP/MAS technique and the spectrum obtained at the longest contact-
time has the same lines as was detected by the MAS technique. Other interest-
 NMR 13C high resolution study of EVA 197

200 400 600 800

-Ad

-t w
--AL
loo0
_LL
2ooo 4ooo 80@3

Fig. 4. Ordering of contact time of EVA.

ing information extracted from this experiment was the value of proton spin-
lattice relaxation time in the rotating frame calculated only for the NMR line
at 33.0 ppm; a very small number was obtained, 1 ms. This value confirms
the fact that the rigid domain is formed only by the CH2 sequences (from
rigid ethylene), since the response of each proton linked to the carbon can
give an idea of the homogeneity and the mobility of the domains or microdo-
mains, which was already observed qualitatively.

4 CONCLUSION

The molecular mobility was extracted by both MAS and CP/MAS comparison
and by the form of variable contact time decay, which was confirmed by
proton Tip response.Unlinked BIBs List:4

ACKNOWLEDGEMENTS

The authors would like to thank the PETROBRAS/CENPES/DIQUIM for the

NMR facilities and the Fenorte.
198 G. C. Stael, M. I. B. Tavares

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