In the Laboratory

An Undergraduate Experiment in Polyester (PET) Synthesis

Andrew N. Cammidge* School of Chemical Sciences, University of East Anglia, Norwich NR4 7TJ, UK

At UEA, first-year undergraduate chemistry students are encouraged to take an extra laboratory course if their timetable allows. The current course entitled Macromolecules and Molecular Assemblies is also compulsory for students enrolled on our degree course Chemistry with Advanced Materials. All experiments are chosen to reinforce some fundamental principles of chemistry under this common theme. Experiments in this unit include liquid crystal synthesis, inorganic and organic polymers and colloids. Each experiment is introduced by a one-hour lecture, in which the science and industrial relevance of the experiment is put into context. The laboratory experiments themselves aim to introduce some more advanced practical techniques and encourage independent investigation. An important part of the course is the introduction of polymer science through the synthesis of both organic and inorganic polymers. The polymers chosen are intended to be of relevance to industry (silicones, nylons, etc.). For this reason a laboratory experiment introducing polyesters (1) was required. To our surprise, no suitable undergraduate experiment could be found. This paper details the experiment we developed and incorporated successfully into the first-year laboratory program. The Experiment

Description The most important polyester manufactured industrially is PET (polyethyleneterephthalate). The industrial preparation is a two-step procedure from terephthalic acid and ethane diol (ED). This procedure is not suitable for direct modification to a laboratory experiment (high temperature and pressure), but can be mimicked using a transesterification reaction starting from dimethylterephthalate (DMTP) (Scheme I).
O H3CO O

2
OCH3

HO

OH

O HO O

O OH O

At this stage the students are assembled around the chalkboard to discuss the procedure. They are asked to predict the temperature reading on the thermometer at reflux. The answer is usually ~190 C (bp of ED). By working through the equilibria setup in the reaction, a consensus is reached that the expected temperature is ~65 C (bp of MeOH). The students return to their apparatus to find that the reflux temperature is indeed ~65 C. After fluxing for 30 min the apparatus is cooled and converted to distillation (the Y adapter is kept in place as a crude fractionation column). Heat is reapplied and a measuring cylinder is used to collect methanol. The students are asked to predict the volume of methanol expected (reinforcing basic calculations). When the head temperature reaches 180 C the heat is turned off and the mixture is allowed to cool slightly. The hot solution is decanted from the antibumping granules and left to crystallize. (The experiment can be left at this point.) Crystallization can be induced by scratching the flask or adding water, if necessary. The crystals are filtered off under vacuum for analysis by 1H NMR spectroscopy. (NOTE: another base such as sodium methoxide could be employed, but use of sodium metal makes the procedure conceptually simple and does not interfere with the subsequent calculation of the expected volume of methanol distillate). Polymerization Small samples of the intermediate are dried between filter papers and placed in crucibles or on microscope slides. The samples are heated carefully on a hot-plate, ED is evaporated, and the physical properties of the sample are monitored as the sample is re-cooled. To some preparations, a small crystal of p-toluene sulfonic acid is added during the heating process. This polymerization requires some care to be successful. Low-molecular-weight polymer (oligomer) cools to form waxy, semicrystalline material. Samples left longer (with acid catalyst) form sticky polymeric masses, which cool further to give clear glassy solids. These properties

2 CH3OH

O OH O

O O

O O O

HO O

heat

HO

OH

Scheme I

The intermediate formed in the first step (bis-(2-hydroxyethyl)terephthalate (2, 3) is identical to that formed in the industrial synthesis. In the first step the students assemble reflux apparatus inserting a Y adapter (with thermometer) between the round-bottom flask and condenser. The roundbottom flask is charged with DMTP and excess ED. A small piece of sodium metal is added and the heating mantle is switched on (Fig. 1).
*Email: a.cammidge@uea.ac.uk.

Figure 1. The apparatus: (a) reflux assembly; (b) distillation assembly.

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In the Laboratory

are used to qualitatively monitor polymerization. (Samples left too long simply char.) Students wash the bulk sample with water and dry it thoroughly. A sample is submitted for NMR, which the students discuss in their report.

Procedure Place dimethyl terephthalate (5 g), ethane diol (80 mL) and some antibumping granules in a 250-mL round-bottom flask. Add a small (~0.1-g) piece of sodium metal (CAUTION!). Fit a Y adapter, thermometer, and reflux condenser and heat the mixture to reflux for 45 minutes using a heating mantle. Cool the mixture somewhat and modify the apparatus for distillation, leaving the Y adapter in place for fractional distillation. Distill off the methanol, stopping the collection when the head temperature reaches 180 C. Decant the solution from antibumping granules and allow it to cool. Collect the crystals that form by suction filtration. Dry a sample thoroughly between filter papers and place it in a crucible or on a microscope slide. Heat this strongly on a hot-plate, carefully removing samples from time to time to check their physical properties as they cool. Repeat with another dry sample, this time adding a small crystal of p-toluene sulfonic acid to the molten material. Wash the bulk sample with water and dry thoroughly before submitting a sample for 1H NMR analysis.

Conclusion This experiment is designed to reinforce important concepts in organic chemistry and introduce polymer synthesis. Students are able to observe, in real time, equilibration of a reaction mixture and see how product composition can be determined by removal of one component (methanol) or use of excess reagent (ED). They perform fractional distillations and apply knowledge of the reaction to calculate predicted volume of distillate. (This was the first time these students had performed a distillation.) The NMR of the intermediate allows the concepts of coupling, chemical shift, and integration to be demonstrated. More advanced experiments could involve D2O exchange. Acknowledgments I would like to thank the students of CHE-1H04 for providing feedback on this experiment, and Amy King for running NMR spectra. Literature Cited
1. Billmeyer, F. W. Textbook of Polymer Science, 3rd ed.; Wiley: New York, 1984. 2. Zahn, H.; Krzikalla, R. Makromol. Chem. 1957, 23, 3153. 3. Allan, R. J. P.; Iengar, H. V. R.; Ritchie, P. D. J. Chem. Soc. 1957, 21072113.

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