THERMAL BEHAVIOUR OF PVC AND A POLYHYDROXYBUTYRATE VALERATE COPOLYMER

A. Marcilla*, J.C.Garcia-Quesada, E. Gil, R. Navarro and D. Berenguer

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: antonio.marcilla@ua.es MATERIALS AND METHODS
The PVC resin Etinox 650 supplied by Aiscondel S.A, the plasticizer DINP by BASF, the epoxided soya bean oil Lankroflex E2307 by Akzo Nobel, the calcium stearate by Union Derivan S.A. and the thermal stabilizer Interlite ZP9604 by Akzo Nobel have been employed. The PVC resin, with 60 phr (parts per hundred of resin) of DINP, 5 phr of epoxydized soya bean oil, 2 phr of thermal stabilizer, 1 phr of calcium stearate and different PHBV concentrations were blended in a high-speed mixer until the PVC absorbed all plasticizer. After that, dry blends were processed in a Brabender internal mixer at 170C and then processed at the same temperature in a hot plates press for 10 minutes under a pressure of 10 atm, obtaining 1 mm thickness plastic sheets.

BACKGROUND
Plastics are by far one of the most common materials employed nowadays in almost all the fields of the human activity. Most of the commercial plastics are produced in petrochemical plants, and derived from oil. Once the service life of the plastics has concluded, they are eventually disposed in landfills or their energy is recovered in wastes incineration plants. Nowadays, in our society, there is a rising worry about the carbon dioxide emissions, and their likely effects on the climate change. Under this situation, the presence of commercial plastics on wastes destined to incineration plants involves a direct contribution to dioxide carbon emissions. The substitution of conventional plastics by other bio-based and renewable polymers could palliate in part those emissions. In bibliography the use of different renewable polymers have been reported. It is worth mentioning two of them, due to their good processability and applicability: Poly lactic acid polymers (PLA) and polyhydroxyalcanoates (PHA). PLA plastics are obtained by polymerisation of lactic acid produced by fermentation of biomass, while polyhydroxyalcanoates are directly synthesised by different types of bacteria under certain circumstances. Polyhydroxybutyrate and different copolymers with polyhydroxyvalerate can be obtained, depending on the bacteria employed and culturing conditions. Apart from the renewable aspects of PLA and PHA, both kinds of polymers also present the advantage that certain types of microorganisms present in landfills can successfully degrade them, i.e., they are biodegradable.

PHA VS CONVENTIONAL POLYMERS

ADVANTAGES
Obtained from renewable sources Biodegraded by microorganisms in landfills

DISADVANTAGES
High cost Poor procesability for certain PHA copolymers Some properties are not comparable to those of some conventional polymers
BINARY BLENDS OF CONVENTIONAL AND BIO-BASED POLYMERS

PVC-PHBV BLENDS present a LOW BIODEGRADABILITY.

Results obtained by enzymatic digestion, soil burying or storage in microorganism cultures have led that blends are not biodegraded in the same conditions that pure PHBV suffers such process.

LANDFILL DISPOSAL AND BIODEGRADATION????

PVC-PHBV BLENDS present a LIMITED THERMAL STABILITY, which

makes difficult their reprocessing without detriment in properties. PVC dehydrochlorination and PHBV degradation may occur.

PRIMARY OR SECONDARY RECYCLING?????

Combustion or thermal cracking of PVC-PHBV BLENDS is a possibility to valorise them after their use.

TERTIARY AND QUATERNARY RECYCLING????

PYROLYSIS AND COMBUSTION

Degradation of blends occurs via two apparent steps: 1. A first step at around 270C where three simultaneous processes take place: PHBV degradation, PVC dehydrochlorination and plasticizer loss. 2. A second process at around 450C, where the degradation of dehydrochlorinated PVC occurs. Although the first apparent process is less sensitive to the type of atmosphere, slightly differences are observed, as possible to observe when comparing the behaviour of the 20 phr blend in pyrolysis and combustion.

PYROLYSIS (heating rate: 10 K/min)

100 90 80 pvc-PHB BINARY BLENDS
Weight loss (%)

70 60 50 40 30 20 10

PVC PVC-10 PHBV PHB-20 phr PHBV PVC-40 phr PHBV PVC-50 phr PHBV PHBV

0 200

250

300

350
Temperature (C)

400

450

500

In any case, although the observed behaviour is apparently the addition of the contribution of both types of polymers (i.e. PVC and PHBV), the degradation pattern of blends can not directly calculated from the behaviour of pure components, and some blending effect is observed. Differences between the expected behaviour (calculated from blends composition and curves of pure components) and the observed behaviour become more prominent when PHBV concentration increases as illustrated as an example for pyrolysis curves.
200 0.0 250 300 350 400
200 0.0 -0.2
Weight loss derivative (K )

COMBUSTION (heating rate: 10 K/min)

200 0
100 90 80
Weight loss (%)
Weight loss derivative (K-1)

250

300

350

400

-0.5

Weight loss derivative (K-1)

250

300

350

400

450

500

-1

-0.4 -0.6 -0.8 -1.0 -1.2 -1.4 -1.6 -1.8 -2.0

200 0
PVC PVC-10 phr PHBV PVC-20 phr PHBV PVC-40 phr PHB PVC-50 phr PHBV PHBV

250

300

350

400

450

500

-1
Weight loss derivative (K-1)

-1.0

-1 -2 -3 -4 -5 -6 -7 PVC PVC-10 phr PHBV PVC-20 phr PHBV PVC-40 phr PHBV PVC-50 phr PHBV PHBV
Temperature (C)

-2 -3 -4 -5

70 60 50 40 30 20 10 0 200

PVC PVC-10 PHBV PHB-20 phr PHBV PVC-40 phr PHBV PVC-50 phr PHBV PHBV

-1.5 10 phr PHBV Calculated 10 phr PHBV Experimental -2.0

Temperature (C)

PVC-20 phr PHBV Calculated PVC-20 phr PHBV Experimental

Temperature (C)

200 0.0 -0.5

250

300

350

400

-6 -7
Temperature (C)

Weight loss derivative (K )

-1

-1.0 -1.5 -2.0 50 phr PHBV Calculated -2.5 50 phr PHBV Experimental -3.0
Temperature (C)

250

300

350
Temperature (C)

400

450

500

ACKNOWLEDGEMENTS: The authors wish to thank the financial support provided by INESCOP and UNIVERSIDAD DE ALICANTE (VIGROB099).