Polymerization

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From Wikipedia, the free encyclopedia

Polymer science

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Properties

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Synthesis
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Classification

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Characterization

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An example of alkene
polymerization, in which each styrene monomer's double bond reforms as a single
bond plus a bond to another styrene monomer. The product is polystyrene.
In polymer chemistry, polymerization (American English), or polymerisation (British
English), is a process of reacting monomer molecules together in a chemical reaction to
form polymer chains or three-dimensional networks.[1][2][3] There are many forms of
polymerization and different systems exist to categorize them.

In chemical compounds, polymerization can occur via a variety of reaction mechanisms

that vary in complexity due to the functional groups present in the reactants[3] and their
inherent steric effects. In more straightforward polymerizations, alkenes form polymers
through relatively simple radical reactions; in contrast, reactions involving substitution at
a carbonyl group require more complex synthesis due to the way in which reactants
polymerize.[3] Alkanes can also be polymerized, but only with the help of strong acids.[4]

As alkenes can polymerize in somewhat straightforward radical reactions, they form

useful compounds such as polyethylene and polyvinyl chloride (PVC),[3] which are
produced in high tonnages each year[3] due to their usefulness in manufacturing
processes of commercial products, such as piping, insulation and packaging. In general,
polymers such as PVC are referred to as "homopolymers", as they consist of repeated
long chains or structures of the same monomer unit, whereas polymers that consist of
more than one monomer unit are referred to as copolymers (or co-polymers).[5]

Other monomer units, such as formaldehyde hydrates or simple aldehydes, are able to
polymerize themselves at quite low
temperatures (ca. −80 °C) to Homopolymers
form trimers;[3] molecules consisting
of 3 monomer units, which
can cyclize to form ring cyclic
structures, or undergo further Copolymers
reactions to form tetramers,[3] or 4
monomer-unit compounds. Such small polymers are referred to as oligomers.
[3]
Generally, because formaldehyde is an exceptionally reactive electrophile it
allows nucleophilic addition of hemiacetal intermediates, which are in general short-lived
and relatively unstable "mid-stage" compounds that react with other non-polar
molecules present to form more stable polymeric compounds.

Polymerization that is not sufficiently moderated and proceeds at a fast rate can be very
hazardous. This phenomenon is known as autoacceleration, and can cause fires and
explosions.

Step-growth vs. chain-growth polymerization[edit]

Step-growth and chain-growth are the main classes of polymerization reaction
mechanisms. The former is often easier to implement but requires precise control of
stoichiometry. The latter more reliably affords high molecular-weight polymers, but only
applies to certain monomers.

Step-growth[edit]
Main article: Step-growth polymerization
In step-growth (or step) polymerization, pairs of reactants, of any lengths, combine at
each step to form a longer polymer molecule. The average molar mass increases
slowly. Long chains form only late in the reaction.[6][7]

Step-growth polymers are formed by independent reaction steps between functional

groups of monomer units, usually containing heteroatoms such as nitrogen or oxygen.
Most step-growth polymers are also classified as condensation polymers, since a small
molecule such as water is lost when the polymer chain is lengthened. For
example, polyester chains grow by reaction of alcohol and carboxylic acid groups to
form ester links with loss of water. However, there are exceptions; for
example polyurethanes are step-growth polymers formed from isocyanate and alcohol
bifunctional monomers) without loss of water or other volatile molecules, and are
classified as addition polymers rather than condensation polymers.
Step-growth polymers increase in molecular weight at a very slow rate at lower
conversions and reach moderately high molecular weights only at very high conversion
(i.e., >95%). Solid state polymerization to afford polyamides (e.g., nylons) is an
example of step-growth polymerization.[8]

Chain-growth[edit]
Main article: Chain-growth polymerization
In chain-growth (or chain) polymerization, the only chain-extension reaction step is the
addition of a monomer to a growing chain with an active center such as a free
radical, cation, or anion. Once the growth of a chain is initiated by formation of an active
center, chain propagation is usually rapid by addition of a sequence of monomers. Long
chains are formed from the beginning of the reaction.[6][7]

Chain-growth polymerization (or addition polymerization) involves the linking together of

unsaturated monomers, especially containing carbon-carbon double bonds. The pi-bond
is lost by formation of a new sigma bond. Chain-growth polymerization is involved in the
manufacture of polymers such as polyethylene, polypropylene, polyvinyl chloride (PVC),
and acrylate. In these cases, the alkenes RCH=CH2 are converted to high molecular
weight alkanes (-RCHCH2-)n (R = H, CH3, Cl, CO2CH3).

Other forms of chain growth polymerization include cationic addition

polymerization and anionic addition polymerization. A special case of chain-growth
polymerization leads to living polymerization. Ziegler–Natta polymerization allows
considerable control of polymer branching.

Polymerization of ethylene
Diverse methods are employed to manipulate the initiation, propagation, and
termination rates during chain polymerization. A related issue is temperature control,
also called heat management, during these reactions, which are often highly
exothermic. For example, for the polymerization of ethylene, 93.6 kJ of energy are
released per mole of monomer.[8]

The manner in which polymerization is conducted is a highly evolved technology.

Methods include emulsion polymerization, solution polymerization, suspension
polymerization, and precipitation polymerization. Although the polymer dispersity and
molecular weight may be improved, these methods may introduce additional processing
requirements to isolate the product from a solvent.

Photopolymerization[edit]
Main article: Photopolymer
Most photopolymerization reactions are chain-growth polymerizations which are
initiated by the absorption of visible[9] or ultraviolet light. The light may be absorbed
either directly by the reactant monomer (direct photopolymerization), or else by
a photosensitizer which absorbs the light and then transfers energy to the monomer. In
general, only the initiation step differs from that of the ordinary thermal polymerization of
the same monomer; subsequent propagation, termination, and chain-transfer steps are
unchanged.[6] In step-growth photopolymerization, absorption of light triggers an addition
(or condensation) reaction between two comonomers that do not react without light. A
propagation cycle is not initiated because each growth step requires the assistance of
light.[10]

Photopolymerization can be used as a photographic or printing process because

polymerization only occurs in regions which have been exposed to light. Unreacted
monomer can be removed from unexposed regions, leaving a relief polymeric image.
[6]
Several forms of 3D printing—including layer-by-layer stereolithography and two-
photon absorption 3D photopolymerization—use photopolymerization.[11]

Multiphoton polymerization using single pulses have also been demonstrated for
fabrication of complex structures using a digital micromirror device.[12]

See also