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Polymerization is the formation of long, repeating organic polymer chains.

Polymerization dates back to the beginning of DNA based life, as both DNA and proteins can be considered polymers. The first 'synthetic' polymers of the 19th century were actually formed by modifying natural polymers. For example nitrocellulose was manufactured by reacting cellulose with nitric acid. The first genuinely man-made polymer, bakelite, was synthesized in 1872, however research into polymers and polymerization really accelerated in the 1930s after the serendipitous discovery of polyethene by the chemical company ICI.

There are many forms of polymerization, and different systems exist to categorize them. Categorizations include the addition-condensation system and the chain growth-step growth system. Another form of polymerization is ring-opening polymerization, which is similar to chain polymerization.

Addition polymerization involves the linking together of molecules incorporating double or triple chemical bonds. These unsaturated monomers (the identical molecules which make up the polymers) have extra, internal, bonds which are able to break and link up with other monomers to form the repeating chain. Addition polymerization is involved in the manufacture of polymers such as polyethene, polypropylene and polyvinylchloride (PVC.) A special case of addition polymerization leads to living polymerization.

Condensation polymerization occurs when monomers bond together through condensation reactions. Typically these reactions can be achieved through reacting molecules incorporating alcohol, amine or carboxylic acid (or other carboxyl derivative) functional groups. When an amine reacts with a carboxylic acid an amide or peptide bond is formed, with the release of water (hence condensation polymerization.) This is the process through which amino acids link up to form proteins, as well as how kevlar is formed.

The chain growth-step growth system categorizes polymers based on their mechanism. While most polymers will fall into their similar category from the addition-condensation method of categorization, their are a fwe exceptions.

Chain growth polymers are defined as polymers formed by the reaction of monomer with a reactive center. These polymers grow to high molecular weight at a very fast rate. It is important to note that the overall conversion rates between chain and step growth polymers are similar, but that high molecular weight polymers are formed in addition reactions much more quickly than with step polymerizations.

Step growth polymers are defined as polymers formed by the stepwise reaction between functional groups of monomer. Most step growth polymers are also classified as condensation polymers, but not all step growth polymers (like polyurethanes formed from isocyanate and alcohol bifunctional monomers) release condensates. Step growth polymers increase in molecular weight at a very slow rate at lower conversions and only reach moderately high molecular weights at very high conversion (i.e. >95%).

To alleviate inconsistencies in these naming methods, adjusted definitions for condensation and addition polymers have been developed. A condensation polymer is defined as a polymer that involves elimination of small molecules during its synthesis, or contains functional groups as part of its backbone chain, or it repeat unit does not contain all the atoms present in the hypothetical monomer to which it can be degraded.

Addition polymerization

Addition polymerization involves the breaking of double or triple bonds, which are used to link monomers in to chains. In the polymerization of ethene (fig. 1), its double bond is broken and it is used to bond to another poly(ethene) monomer. There are several mechanisms through which this can be initiated. The free radical mechanism was one of the first methods to be used. Free radicals are very reactive atoms or molecules which have unpaired electrons. Taking the polymerization of ethene as an example, the free radical mechanism can be divided in to three stages: initiation, propagation and termination.

Initiation is the creation of free radicals necessary for propagation. The radicals can be created from organic peroxide molecules, molecules containing an O-O single bond, by reacting oxygen with ethene. The products formed are unstable and easily break down into two radicals. In an ethene monomer, one electron pair is held securely between the two carbons in a sigma bond. The other is more loosely held in a pi bond. The free radical uses one electron from the pi bond to form a more stable bond with the carbon atom. The other electron returns to the second carbon atom, turning the whole molecule in to another radical.

Propagation is the rapid reaction of this radicalised ethene molecule with another ethene monomer, and the subsequent repetition to create the repeating chain.

Termination only occurs when two radical chains collide. The lone electrons pair up and a stable molecule is formed, the product being a sum of the individual polymer chains.

Free radical addition polymerization must take place at high temperatures and pressures, approximately 300°C and 2000 At. There are problems with the lack of control in the reaction, specifically with the creation of variably branched chains. Also, as termination occurs randomly, when two chains collide, it is impossible to control the length of individual chains. Finally, reactions involving larger molecules such as polypropene are difficult. For this reason new mechanisms for addition polymerization were developed. An early replacement was the Ziegler-Natta catalyst.

The problem of branching occurs during propagation, when a chain curls back on itself and breaks - leaving irregular chains sprouting from the main carbon backbone. Branching makes the polymers less dense and results in low tensile strength and melting points. Developed by Karl Ziegler and Giulio Natta in the 1950s, Ziegler-Natta catalysts (triethylaluminium in the presence of a metal (IV) chloride) largely solved this problem. Instead of a free radical reaction, the initial ethene monomer inserts between the aluminium atom and one of the ethyl groups in the catalyst. The polymer is then able to grow out from the aluminium atom and results in almost totally unbranched chains. With the new catalysts, the tacticity of the polypropene chain, the alignment of alkyl groups, was also able to be controlled. Different metal chlorides allowed the selective production of each form i.e., syndiotactic, isotactic and atactic polymer chains could be selectively created.

However there were further complications to be solved. If the Ziegler-Natta catalyst was poisoned or damaged then the chain stopped growing. Also, Ziegler-Natta monomers could be only small, and it was impossible to control the molecular mass of the polymer chains. Again new catalysts, the metallocenes, were developed to tackle these problems. Due to their structure they have less premature chain termination and branching.

Condensation polymerization

A polymerization which occurs by the process of a condensation reaction.

See also: Polymer -- Zieglar-Natta catalyst -- Metallocene