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Polymerization

Similarly to alkenes, polyenes may undergo polymerization. For example, 1,3-butadiene can polymerize either by normal (1,2) or conjugated (1,4) addition. The two processes lead to different polymers, more or less branched, with different physical and chemical properties.

1,2- and 1,4-polymerization of 1,3-butadiene

Polymerization controlled by Ziegler-Natta catalysis yields polymers of everyday use (tyres, coatings, etc.).

Ziegler-Natta polymerization of isoprene to (Z)-polyisoprene and of chloroprene to neoprene

In order to give additional elasticity to these polymers, vulcanization is performed. This procedure consists of the treatment of the polymer with sulfur under heating. The polymer chains end up interconnected by polysulfide bridges, which give it added elasticity.

Natural rubber (caoutchouc) is produced by some trees native to the Amazon rainforest. The polymerization is performed by certain enzymes from natural isoprene derivatives.

Terpene biosynthesis: isopentenyl pyrophosphate joins dimethylallyl pyrophosphate to give geranyl pyrophosphate (C₁₀) and then farnesyl pyrophosphate (C₁₅)

Some natural products essential to life, like cholesterol or in general the family of terpenes, are produced by biologically controlled polymerization of polyenic systems:

Enzymatic cyclization of squalene (C30 triterpene) to the cholesterol precursor