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# Polymerization

For polymerization in DNA, see DNA polymerase.

In polymer chemistry, polymerization is a process of bonding monomers, or "single units" together through a variety of reaction mechanisms to form longer chains named polymers. Polymers exist as a variety of 3-dimensional shapes[1], each with specific individual properties relevant to the monomers or reaction mechanisms they are formed from.

## Introduction

 Single-monomer formed polymers $A + A + A... \rightarrow AAA ...$ Co-polymers $A + B + A... \rightarrow ABA ...$

In chemical compounds, polymerization occurs via a variety of reaction mechanisms which vary in complexity due to functional groups present in reacting compounds[2] and their inherent steric effects explained by VSEPR Theory. In more straightforward polymerization, alkenes, which are a relatively stable due to σ bonding between carbon atoms form polymers through relatively simple radical reactions; conversely, more complex reactions such as those that involve substitution at the carbonyl atom require more complex synthesis due to the way in which reacting molecules polymerize.[2]

As alkenes can be formed in somewhat straightforward reaction mechanisms, they form useful compounds such as polyethylene and polyvinyl chloride (PVC) when undergoing radical reactions,[2] which are produced in high tonnages each year[2] due to their usefulness in manufacturing processes of commercial products, such as piping, insulation and packaging. Polymers such as PVC are generally referred to as "singular" polymers as they consist of repeated long chains or structures of the same monomer unit, whereas polymers that consist of more than one molecule are referred to as "co-polymers".

Other monomer units, such as formaldehyde hydrates or simple aldehydes, are able to polymerize themselves at quite low temperatures (>-80oC) to form trimers;[2] molecules consisting of 3 monomer units which can cyclize to form ring cyclic structures, or undergo further reactions to form tetramers,[2] or 4 monomer-unit compounds. Further compounds either being referred to as oligomers[2] in smaller molecules. Generally, because formaldehyde is an exceptionally reactive electrophile it allows nucleophillic addition of hemiacetal intermediates, which are generally short lived and relatively unstable "mid stage" compounds which react with other molecules present to form more stable polymeric compounds.

Polymerization that is not sufficiently moderated and proceeds at an undesirably fast rate can be very hazardous. This phenomenon is known as Hazardous polymerization and can cause fires and explosions.

## Chain-growth

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 polyethylene, polypropylene and polyvinyl chloride (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, there are a few 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.

Addition polymerization involves the breaking of double or triple bonds, which are used to link monomers into chains. In the polymerization of ethylene, its pi bond is broken and these two electrons rearrange to create a new propagating center like the one that attacked it. The form this propagating center takes depends on the specific type of addition mechanism. 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 ethylene 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 radical initiators, such as organic peroxide molecules, molecules containing an O-O single bond, by reacting oxygen with ethylene. 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 radicalized ethylene molecule with another ethylene monomer, and the subsequent repetition to create the repeating chain.

Termination occurs when a radical reacts in a way that prevents further propagation. The most common method of termination is by coupling where two radical species react with each other forming a single molecule. Another, less common method of termination is disproportionation where two radicals meet, but instead of coupling, they exchange a proton, which gives two terminated chains, one saturated and the other with a terminal double bond.

Free radical addition polymerization of ethylene must take place at high temperatures and pressures, approximately 300°C and 2000 At. While most other free radical polymerizations do not require such extreme temperatures and pressures, they do tend to lack control. One effect of this lack of control is a high degree of branching. Also, as termination occurs randomly, when two chains collide, it is impossible to control the length of individual chains. A newer method of polymerization similar to free radical, but allowing more control involves the Ziegler-Natta catalyst especially with respect to polymer branching.

Other forms of addition polymerization include cationic addition polymerization and anionic addition polymerization. While not used to a large extent in industry yet due to stringent reaction conditions such as lack of water and oxygen, these methods provide ways to polymerize some monomers that cannot be polymerized by free radical methods such as polypropylene. Cationic and anionic mechanisms are also more ideally suited for living polymerizations, although free radical living polymerizations have also been developed.

## Step-growth

Step growth polymers are defined as polymers formed by the stepwise reaction between functional groups of monomers. 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 its repeat unit does not contain all the atoms present in the hypothetical monomer to which it can be degraded.