THERMAL DEGRADATION OF CROSSLINKED POLYETHYLENE

A. Marcilla, J.C.Garcia-Quesada, E. Gil, D. Berenguer, R. Navarro, R.Ruiz-Femenia and M. Lopez-Pastor*

Chemical Engineering Department University of Alicante. P. O. Box 99, E-03080 Alicante, Spain. Tlf.: +34 965 90 34 00 - Ext. 3789, Fax: +34 965 90 38 26, *E-mail: miriam3684@hotmail.com
ABSTRACT
Polyethylene is the most common plastic employed nowadays. For example around 30% of plastics consumed in 2006 in the European Union were low density polyethylene (LDPE) and high density polyethylene (HDPE) (1). Polyethylenes were followed in consumption by polypropylene (19%) and PVC (13%). Although the thermoplastic aspect of polyethylene could be considered as a relevant advantage from the point of view of its likely recycling, it is actually a disadvantage from the point of view that mechanical properties drop when the temperature approaches the melting point. In order to improve mechanical properties of polyethylene at relatively high temperatures, it can be crosslinked by different types of chemicals as silanes or peroxides. Under this situation, polyethylene becomes an elastomeric material and its recycling is not possible unless it is valorised in order to recover its energy by combustion or pyrolysis, and in consequence the study of such processes is of practical interest. In previous works (2), the thermogravimetric behaviour in inert atmosphere of a crosslinked LLDPE was analysed. Results obtained in a thermobalance showed a minor dependence with peroxide concentration, in spite of the fact that gel content (that is a measurement of crosslinking efficiency) may suffer relevant changes.
ACKNOWLEDGEMENTS: The authors wish to thank the Generalitat Valenciana (GVPRE/2008/148), Universidad de Alicante (VIGROB099).

In the present work compounds produced in a pyrolyzer Pyroprobe have been fed to a Gas Chromatograph, allowing the qualitative analysis of the composition of gases produced during the decomposition of different samples. Results obtained have revealed that although thermograms are almost identical, it is possible to observe differences in the chromatograms associated to changes in the product distribution, depending on the crosslinking yield.

MATERIALS AND SAMPLE PREPARATION

The Lotrene A15 from QUAPCO, with a melt index of 15 g/10 min and a density of 918 kg/m3, was used. The crosslinking agent employed was di-tert-butyl peroxide (>98% purity), provided by Merck. The polymer with different quantities of peroxide (expressed in phr, parts in weight per hundred of resin) were blended in a Brabender Plasticorder Mixer PL2000 at a temperature of 140C and a speed of 40 rpm for 5 min. Afterwards, all samples were compressed at 200C and 20 bar for 20 min, obtaining sheets of 2 mm of thickness.

METHODS
CALORIMETRY A Perkin Elmer Pyris 6 DSC Calorimeter was used to perform Differential Scanning Calorimetry analyses on the samples in a flowing nitrogen atmosphere (99.99% minimum purity) with a flow rate of 20 mL/min (STP). Samples were heated from 40 to 220C at 10C/min and then cooled from 220 to 40C at 5C/min. GEL CONTENT The extent of the crosslinking of the samples was determined through gel content measurements, according to ASTM D 2765. Approximately 0.6 g of each sample were exactly weighed and placed in a cellulose bag, which later underwent Soxhlet extraction for 24 h using p-xylene as solvent. After the extraction, the bags were dried in a oven at 80C until constant weight is achieved. Then gel content is calculated as the fraction of the remaining polymer after extraction.

THERMOGRAVIMETRY Samples consisting in uncrosslinked (PE) and crosslinked polyethylene (XPE) were heated in a Mettler Toledo TGA/SDTA851e thermo-balance, using a heating rate of 10C/min from 30 to 700C. The atmosphere used was nitrogen (99.99% minimum purity) with a flow rate of 50 mL/min (STP). PYROPROBE REACTOR EXPERIMENTS A Pyroprobe 2500 equipment supplied by CDS Analytical INC was connected online with a Gas Chromatograph Agilent GC 6890N adapted with a Flame Ionization Detector (FID) and a column HP-5MS (30 m 0.32 mm I.D.). The Pyroprobe reactor was heated up to 700C, and then kept at such temperature for 20 s.

91

R-O-O-R

Crystallization temperature (C)

80 70 60

Gel content (%)

HHHHHH -C-C-C-C-C-C-

HHHHHH -C-C-C-C-C-C-

90 89 88 87 86 85 84 83

50 40 30 20 10

2 R-O
+

HH
+

HH
H H

HH
HH

HH
H H

PE

1DCP

2DCP

3DCP

4DCP

0 Pure LDPE 1 phr 2 phr 3 phr 4 phr Peroxide concentration (phr)

Peroxide concentration (phr)

100 90 80
Weight loss (%)

HHHHHH 2 -C-C-C-C-C-CHHHHHH
PEROXIDE+POLYETHYLENE (PE)

HH

70 60 50 40 30 20 10 0
Pure PE 2 phr DCP 4phr DCP

-C-C-C-C-C-CHHHHHH

-C-C-C-C-C-CHHHHHH
CROSSLINKED POLYETHYLENE (XPE)

300

350

400

450

500

550

600

Temperature (C)

CROSSLINKING HAS OCURRED, BUT THERMOGRAVIMETRIC RESULTS ARE VERY SIMILAR

CONCLUSIONS
Ratio Diene/Alkene

1.5 1.4 1.3 1.2

1. Samples with different crosslinked degree have been obtained according to gel content and calorimetric results. 2. Thermogravimetric behaviour of samples with a different crosslinking yield is similar, in good agreement with bibliography. These results could apparently indicate that pyrolysis degradation pattern is similar in all cases. 3. In spite of such similar thermogravimetric behaviour, the chemical nature of gases evolved are readily affected by crosslinking, since it enhances the formation of dienes versus alkanes and alkenes.

1.1 1.0 0.9 0.8 0.7 0.6 0.5 0 phr 1 phr 2 phr 3 phr Peroxide concentration 4 phr

1.2

DOES IT MEAN THAT PYROLYSIS DEGRADATION PATTERN IS INDEPENDENT OF CROSSLINKING?

1.0

Ratio Alkane/Alkene

0.8

BIBLIOGRAPHY
1. Association of plastics manufacturers. The Compelling Facts about Plastics - An analysis of plastics production, demand and recovery for 2006 in Europe. January 2008. (Available on http://www.plasticseurope.org). 2. A. Marcilla, R. Ruiz-Femenia, J. Hernndez and J.C. Garca-Quesada. J. Anal. Appl. Pyrol. 76 (2006), pp. 254-259.

0.6

0.4

0.2

0.0 0 phr 1 phr 2 phr 3 phr Peroxide concentration 4 phr