Conjugated dienes (alkenes with two double bonds and a single bond in between) can be polymerized to form important compounds like rubber. This takes place, in different forms, both in nature and in the laboratory. Interactions between double bonds on multiple chains leads to cross-linkage which creates elasticity within the compound.
Polymerization of 1,3-Butadiene
For rubber compounds to be synthesized, 1,3-butadiene must be polymerized. Below is a simple illustration of how this compound is formed into a chain. The 1,4 polymerization is much more useful to polymerization reactions.
Above, the green structures represent the base units of the polymers that are synthesized and the red represents the bonds between these units which form these polymers. Whether the 1,3 product or the 1,4 product is formed depends on whether the reaction is thermally or kinetically controlled.
Natural rubber is an addition polymer that is obtained as a milky white fluid known as latex from a tropical rubber tree. Natural rubber is from the monomer isoprene (2-methyl-1,3-butadiene), which is a conjugated diene hydrocarbon as mentioned above. In natural rubber, most of the double fonds formed in the polymer chain have the Z configuration, resulting in natural rubber's elastomer qualities.
Charles Goodyear accidentally discovered that by mixing sulfur and rubber, the properties of the rubber improved in being tougher, resistant to heat and cold, and increased in elasticity. This process was later called vulcanization after the Roman god of fire. Vulcanization causes shorter chains to cross link through the sulfur to longer chains. The development of vulcanized rubber for automobile tires greatly aided this industry.
The most important synthetic rubber is Neoprene which is produced by the polymerization of 2-chloro-1,3-butadiene.
In this illustration, the dashed lines represent repetition of the same base units, so both the products and reactants are polymers. The reaction proceeds with a mechanism similar to the Friedel-Crafts mechanism. Cross-linkage between the chlorine atom of one chain and the double bond of another contributes to the overall elasticity of neoprene. This cross-linkage occurs as the chains lie next to each other at random angles, and the attractions between double bonds prevent them from sliding back and forth.
- Vollhardt, Peter, and Neil E. Schore. Organic Chemistry: Structure and Function. New York: W. H. Freeman & Company, 2007.
- Buehr, Walter. Rubber: Natural and Synthetic. Morrow, 1964.
10. Draw out the mechanism for the natural synthesis of rubber from 3-methyl-3-butenyl pyrophosphate and 2-methyl-1,3-butadiene. Show the movement of electrons with arrows.
11. Draw a segment for the polymer that may be made from 2-tert-butyl-1,3-butadiene.
12. Propose the mechanism for the acid catalyzed polymerization of 2-methyl-1,3-butadiene.
12. The initial step is an addition of a hydrogen from the acid, followed by the polymerization.
Prof. Steven Farmer (Sonoma State University)