13/03/2018 Polymerization - Wikipedia

Polymerization
IUPAC definition
polymerization: The process of converting a monomer or a mixture of monomers into a polymer.[1]

In polymer chemistry, polymerization is a

process of reacting monomer molecules
together in a chemical reaction to form
polymer chains or three-dimensional
networks.[2][3][4] There are many forms of
polymerization and different systems exist An example of alkene polymerization, in which each styrene
to categorize them. monomer's double bond reforms as a single bond plus a bond to
another styrene monomer. The product is polystyrene.

Contents
Introduction
Step-growth
Chain-growth
Physical polymer reaction
engineering
Photopolymerization
See also
References

Introduction
In chemical compounds, polymerization occurs via a variety of
Homopolymers
reaction mechanisms that vary in complexity due to functional groups
present in reacting compounds[4] and their inherent steric effects. In
more straightforward polymerization, alkenes form polymers through
relatively simple radical reactions; in contrast, more complex reactions Copolymers
such as those that involve substitution at the carbonyl group require
more complex synthesis due to the way in which reacting molecules
polymerize.[4] Alkanes can also be polymerized, but only with the help
of strong acids.[5]

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,[4] which are produced in high tonnages
each year[4] 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 molecule are referred
to as copolymers (or co-polymers).[6]

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

Step-growth
Step-growth polymers are defined as polymers formed by the stepwise reaction between functional groups of
monomers, usually containing heteroatoms such as nitrogen or oxygen. 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; in this case, we talk about addition 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%).

To alleviate inconsistencies in these naming methods, adjusted definition for condensation and addition polymers
have been developed. A condensation polymer is defined as a polymer that involves loss of small molecules during its
synthesis, or contains heteroatoms 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.

Chain-growth
Chain-growth polymerization (or addition polymerization) involves the linking together of molecules incorporating
double or triple carbon-carbon bonds. These unsaturated monomers (the identical molecules that make up the
polymers) have extra internal bonds that are able to break and link up with other monomers to form a repeating chain,
whose backbone typically contains only carbon atoms. Chain-growth polymerization is involved in the manufacture of
polymers such as polyethylene, polypropylene, and polyvinyl chloride (PVC). A special case of chain-growth
polymerization leads to living polymerization.

In the radical polymerization of ethylene, its π bond is broken, and the 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 is
one of the first methods to be used. Free radicals are very reactive atoms or molecules that have unpaired electrons.
Taking the polymerization of ethylene as an example, the free radical mechanism can be divided into three stages:
chain initiation, chain propagation, and chain termination.

Free radical addition polymerization of ethylene must take place at high

temperatures and pressures, approximately 300 °C and 2000 atm. While
most other free radical polymerizations do not require such extreme Polymerization of ethylene
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.

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Other forms of chain growth 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.

Esters of acrylic acid contain a carbon-carbon double bond which is conjugated to an ester group. This allows the
possibility of both types of polymerization mechanism. An acrylic ester by itself can undergo chain-growth
polymerization to form a homopolymer with a carbon-carbon backbone, such as poly(methyl methacrylate). Also,
however, certain acrylic esters can react with diamine monomers by nucleophilic conjugate addition of amine groups
to acrylic C=C bonds. In this case the polymerization proceeds by step-growth and the products are poly(beta-amino
ester) copolymers, with backbones containing nitrogen (as amine) and oxygen (as ester) as well as carbon.[7]

Physical polymer reaction engineering

To produce a high-molecular-weight, uniform product, various methods are employed to better control the initiation,
propagation, and termination rates during chain polymerization and also to remove excess concentrated heat during
these exothermic reactions compared to polymerization of the pure monomer (also referred to as bulk
polymerization). These include emulsion polymerization, solution polymerization, suspension polymerization, and
precipitation polymerization. Although the polymer polydispersity and molecular weight may be improved, these
methods may introduce additional processing requirements to isolate the product from a solvent.

Photopolymerization
Most photopolymerization reactions are chain-growth polymerizations which are initiated by the absorption of
visible 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.[8] 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.[9]

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.[8] Several forms of 3D printing—including layer-by-layer stereolithography and two-photon
absorption 3D photopolymerization—use photopolymerization.

Multiphoton polymerization using single pulses have also been demonstrated for fabrication of complex structures
using a digital micromirror device.[10]

See also
Addition polymer Polymer characterization Ring-opening polymerization
Condensation polymer Polymer physics Sequence-controlled polymers
Cross-link Reversible Sol-gel
Metallocene addition−fragmentation chain Ziegler-Natta catalyst
transfer polymerization
Plasma polymerization

References

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1. Jenkins, A. D.; Kratochvíl, P.; Stepto, R. F. T.; Suter, U. W. (1996). "Glossary of basic terms in polymer science
(IUPAC Recommendations 1996)" (https://www.iupac.org/publications/pac/1996/pdf/6812x2287.pdf) (PDF). Pure
and Applied Chemistry. 68 (12): 2287–2311. doi:10.1351/pac199668122287 (https://doi.org/10.1351%2Fpac1996
68122287). See definition 3.1, p. 2305.
2. Young, R. J. (1987) Introduction to Polymers, Chapman & Hall ISBN 0-412-22170-5
3. International Union of Pure and Applied Chemistry, et al. (2000) IUPAC Gold Book, Polymerization (http://goldbo
ok.iupac.org/P04740.html)
4. Clayden, J., Greeves, N. and Warren, S. (2000). Organic chemistry (https://books.google.com/books?id=kQgu2j_
ber0C&printsec=frontcover), Oxford University Press ISBN 0198503466 pp. 1450–1466
5. Roberts, Durward T., JR. and Lawrence E. Calihan. "Polymerization (Polycondensation) of Alkanes over
Fluosulfonic Acid and Antimony Pentafluoride (http://www.tandfonline.com/doi/abs/10.1080/00222337308066378?
journalCode=lmsa19)". Journal of Macromolecular Science: Part A - Chemistry Vol. 7 , Iss. 8, 1973
6. Cowie, J.M.G. (1991) Polymers: Chemistry and Physics of Modern Materials, Chapman and Hall, p. 4
ISBN 0849398134
7. Lynn, David M.; Langer, Robert (2000). "Degradable Poly(β-amino esters):  Synthesis, Characterization, and Self-
Assembly with Plasmid DNA". Journal of the American Chemical Society. 122 (44): 10761.
doi:10.1021/ja0015388 (https://doi.org/10.1021%2Fja0015388).
8. Allcock H.R., Lampe F.W. and Mark J.F. Contemporary Polymer Chemistry (3rd ed. Pearson Prentice-Hall 2003),
chap.5. ISBN 0-13-065056-0
9. Soto, Marc; Sebastián, Rosa María; Marquet, Jordi (2014). "Photochemical Activation of Extremely Weak
Nucleophiles: Highly Fluorinated Urethanes and Polyurethanes from Polyfluoro Alcohols" (http://pubs.acs.org/doi/
abs/10.1021/jo5005789). J. Org. Chem. 79: 5019–5027. doi:10.1021/jo5005789 (https://doi.org/10.1021%2Fjo500
5789).
10. Mills, Benjamin; Grant-Jacob, James A; Feinaeugle, Matthias; Eason, Robert W (2013-06-17). "Single-pulse
multiphoton polymerization of complex structures using a digital multimirror device" (https://doi.org/10.1364/OE.2
1.014853). Optics Express. 21 (12). Bibcode:2013OExpr..2114853M (http://adsabs.harvard.edu/abs/2013OExpr..
2114853M). doi:10.1364/oe.21.014853 (https://doi.org/10.1364%2Foe.21.014853). ISSN 1094-4087 (https://www.
worldcat.org/issn/1094-4087).

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