APPENDIX 9.

DETERMINATION OF THE CROSS-LINK DENSITY OF RUBBER

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APPENDIX 9.3 DETERMINATION OF THE CROSS-LINK DENSITY OF RUBBER BY SWELLING TO EQUILIBRIUM The present experiment is based on the rapid swelling of elastomers by organic solvents. Application of the FloryRehner equation yields the number of active network chain segments per unit volume, a measure of the extent of vulcanization (C1,C2). Experiment Time: About 1 hour Level: Physical Chemistry Principles Illustrated: 1. The cross-linked nature of rubber 2. Diffusion of a solvent into a solid Equipment and Supplies: One large rubber band One 600-ml beaker (containing 300 ml toluene) One ruler or yardstick One long tweezers to remove swollen rubber band Paper towels to blot wet swollen rubber band One clock or watch One lab bench First, cut the rubber band in one place to make a long rubber strip. Measure and record its length in the relaxed state. Place in the 600-ml beaker with toluene, making sure the rubber band is completely covered. Remove after 5 to 10 minutes. Blot dry. Caution: toluene is toxic and can be absorbed through the skin. Again, measure and record length. Repeat for about 1 hour. Optional: Cover and store overnight. Measure the length of the band the next day. Expected Results The rubber band swells to about twice its original length, but then it remains stable. Note that swelling to twice its length means a volume increase of about a factor of 8. Also, note that the swollen rubber band is much weaker than the dry material and may break if not treated gently.

Reprinted in part from L. H. Sperling and T. C. Michael, J. Chem. Ed., 59, 651 (1982).

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CROSS-LINKED POLYMERS AND RUBBER ELASTICITY

Chemically most rubber bands and similar materials are composed of a random copolymer of butadiene and styrene, written poly(butadienestat styrene), meaning that the placement of the monomer units is statistical along the chain length. Usually this product is made via emulsion polymerization.
Swelling of a Rubber Band with Time Length, cm 16.5 24.0 26.0 27.0 28.0 Time, min 0 14 25 36 70

Typical results are shown in the table. Over a period of 70 minutes, the length of the rubber band increased from 16.5 to 28.0 cm, for a volume increase of about 4.9. This is sufciently visible to be seen at the back of an ordinary classroom. The rubber band would continue to swell slowly for some hours, or even days, but for the purposes of demonstrations and classroom calculations, the swelling can be considered nearly complete.

Calculations For the system poly(butadienestatstyrene) and toluene, c1 is 0.39. Assuming that additivity of volumes v2 is found from the swelling data to be 0.205. The quantity V1 is 106.3 cm3/mol for toluene. Algebraic substitution into equation (9.92) yields n equal to 1.55 10-4 mol/cm3. (Compare result with Appendix 9.2.)

Extra Credit Two experiments (or demonstrations) can be done easily for extra credit. 1. Obtain some unvulcanized rubber. Most tire and chemical companies can supply this. Put a piece of this material into toluene overnight and observe the results. It should dissolve to form a uniform solution. 2. The quantity n can be used also to predict Youngs modulus (the stiffness) of the rubber band. The equation is E = 3nRT (A9.2.1)

where E represents Youngs modulus, and R in these units is 8.31 107 dynescm/molK. For the present experiment, E is calculated to be 1.1 107 dynes/cm2, typical of such rubbery products.