Encyclopedia of Polymeric Nanomaterials

DOI 10.1007/978-3-642-36199-9_237-1
# Springer-Verlag Berlin Heidelberg 2014

Monomers, Oligomers, Polymers, and Macromolecules (Overview)

Kensuke Naka*
Department of Chemistry and Materials Technology, Graduate School of Science and Technology, Kyoto Institute of
Technology, Sakyo-ku/Kyoto, Japan

Synonyms
Macromolecule; Polymer; Polymer molecule

Definition
A polymer is a molecule of high molecular weight, the structure of which essentially comprises the
multiple repetition of units derived, actually or conceptually, from molecules of low molecular
weight. Polymers range from synthetic polymers to natural biopolymers such as DNA and proteins.
An oligomer is a molecule that consists of a few monomer units. “Macromolecule” is used for
individual molecules of high molecular weight and “polymer” is used to denote a substance
composed of macromolecules.

Introduction
Polymeric materials have existed as fundamental components of plants and animals from time
immemorial. The human beings have used these natural polymeric materials in food, clothing, and
houses from the most ancient times and have then developed synthetic materials such as Celluloid ®,
Bakelite ®, rayon, and rubber [1]. However, we did not know real structures of these polymeric
materials before the beginning of the last century. In 1920, Staudinger proposed a pioneering
polymeric theory that polymers are composed of a linear molecule having high molecular weight,
not aggregates of low molecular weight compounds [2]. Thereafter, basic polymer chemistry such as
the study of radical polymerization and synthesis of nylon was established in 1940. Important
discoveries, i.e., polymer physical chemistry by Flory, Ziegler-Natta catalyst, living polymerization
by Szwarc, promoted polymer science and industry. Polymers are used as plastics and elastomers,
films, and fibers in areas as diverse as clothing, car tires, compact discs, packaging materials, and
prostheses. Moreover, important applications in electroluminescent integrated optic devices and
medical materials such as artificial internal organs have also been developed. The massive growth in
the use of the polymeric materials in the past 70 years can mainly be attributed to their ease of
preparation, lightweight nature, and unique ease of fabrication. Their ease of preparation is a
consequence of using well-established reaction of organic chemistry.

*Email: kenaka@kit.ac.jp

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Encyclopedia of Polymeric Nanomaterials
DOI 10.1007/978-3-642-36199-9_237-1
# Springer-Verlag Berlin Heidelberg 2014

Monomer
A polymer is made by polymerization of monomers in regular and repeating fashion. The monomer
is a small molecule, which can undergo polymerization, thereby contributing constitutional units to
the essential structure of a macromolecule. Therefore, polymer nomenclature is generally based
upon a type of a monomer residue comprising a polymer. For examples, polystyrene and poly
(ethylene oxide) are prepared by polymerization of styrene and ethylene oxide, respectively. Poly-
mers that contain only a single type of repeat unit are known as homopolymers, while a polymer
containing a mixture of repeat units is known as a copolymer.
Three general kinds of monomers, difunctional monomers, unsaturated monomers, and cyclic
rings, can be used for polymerization. Several examples are shown in Fig. 1. Difunctional monomers
such as diamines and diols are employed for polycondensation and polyaddition that involve
exploitation of the functional group chemistry of organic molecules. Unsaturated monomers such
as vinyl monomers, dienes, and acetylenes are used for addition polymerization. In this

Polycondensation
O O
H H
HOOC R COOH + H2N R' NH2 C R C N R' N
–H2O n
Polyaddition O O
O C N R N C O + HO R' OH C NH R NH C O R' O
n

O O O O
H2N NH2 NH NH
Cl Cl –HCl
+ n

CH3 CH3 O
O –HCl
HO C OH + Cl C Cl O C O C
n
CH3 CH3

Addition polymerization
CH2 CH CH2 CH
n
X X
CH3

CH2 CH CH2 C CH2 CH CH2 CH CH2 CH CH2 CH2

C O C O CN O
OCH3 OCH3 C O CH2 CCl2
CH2 CH
CH3
Cl

ring-opening polymerization
Cm X Cm X
n

O
O S O C O
O O
NH
O

Fig. 1 Several examples of monomers for polymerization

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Encyclopedia of Polymeric Nanomaterials
DOI 10.1007/978-3-642-36199-9_237-1
# Springer-Verlag Berlin Heidelberg 2014

polymerization, two new C–C single bonds are created in place of one carbon-carbon unsaturated
bond. Cyclic rings such as ethylene oxide and propylene oxide are used for ring-opening polymer-
ization. In the later two monomers, highly reactive intermediate species such as free radical,
carbanion, and carbocation, which are not involved in the monomers, are generated at the propa-
gating ends of the polymers. On the contrary, end groups of polymers by polycondensation and
polyaddition are the same as those of monomers.

Polymer and Macromolecule

The words “polymer” and “macromolecule” are normally used in the same meaning. However, it
should be noted that “polymer” used as a term is ambiguous; it is commonly employed to refer to
both polymer substances and polymer molecules. “Macromolecule” is used for individual molecules
of high molecular weight and “polymer” is used to denote a substance composed of macromole-
cules. “Polymer molecule” can be usually used for a molecule whose structure is composed of
multiple repeating units derived from monomers. Their consequently large molecular weight
relative to small molecular compounds produces unique physical properties, including softness
(rubber elasticity) in elastomers and glassy behavior (liquid-like structure in the solid state) in
plastics.
Most of the physical properties of polymers depend on their molecular weights, M. Some
synthetic polymers can form crystalline, and the crystallization ability of polymers is strongly
related with their tacticity (see section “Control of Polymer Structure” for tacticity). For example,
atactic polystyrene is imperfect due to its long chain-like structure. The degree of crystallinity
typically ranges between 10 % and 80 %, and hence crystallized polymers are often called
“semicrystalline.”
“The glass transition temperature,” Tg, is an important property characterizing amorphous poly-
mers or amorphous phase in semicrystalline, at which the amorphous phase undergoes a transition
from a rubbery or viscous liquid to a hard glassy solid on cooling. Tg of a polymer depends on its
molecular weight because chain ends have higher mobility. This is particularly true for low
molecular weight region (typically M < 104) where Tg increases with increasing molecular weight.
At high molecular weight region, Tg is essentially insensitive to molecular weight. For many
polymers, the molecular weight dependence of Tg can be written in the form Tg ¼ Tg  A/M,
where Tg and A are constants.
Long polymer chains can entangle with each other. “Entanglements” are an important concept in
polymer science to understand the mechanical properties of polymer. For example, the
M dependence of viscosity, , of polymeric liquids varies depending on the existence of entangle-
ments, from  / M (non-entangled) to  / M3.4~3.5 (entangled). This is because entanglements
significantly restrict the polymer chain motion depending on chain length and remarkably retard the
flow. Entanglements are also important for toughness in the glassy state. Low molecular weight
polymers without entanglements are very brittle in the glassy state.

Oligomer
Polymer means a substance composed of a molecule of high molecular weight (generally more than
ten thousand). This is because polymers having a high molecular weight more than ten thousand
show polymer-like properties such as film and fiber forming, and the addition or removal of one or a

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Encyclopedia of Polymeric Nanomaterials
DOI 10.1007/978-3-642-36199-9_237-1
# Springer-Verlag Berlin Heidelberg 2014

few of the units has a negligible effect on the properties. On the other hand, a material with regular
repeating structure but too low an average molecular weight to achieve their properties is usually
called an oligomer. In other words, oligomer is a molecule that consists of a few monomer units.
Dimers, trimers, and tetramers are, for example, oligomers respectively composed of two, three, and
four monomers. The oligomer is regarded as having an intermediate molecular weight if it has
properties which do vary significantly with the removal of one or a few of the units. Although the
molecular mass of oligomer is generally considered several thousands or less, the boundary between
oligomer and polymer is ambiguous.

Characteristic of Polymer Molecules

Synthetic polymer molecules are mixtures of compounds composed of the same repeating structure
units but differing in molecular weight. Thus, polyethylene, for example, has the repeat unit
structure as shown in Fig. 2, where n is the number average degree of polymerization, i.e., the
average number of repeat units per molecule. There is always a molecular weight distribution around
an average value.
Synthetic polymer molecules are also mixtures of linear and branched structures (Fig. 2). It is well
known that mechanical properties of polyethylenes significantly depend on variables such as the
extent and type of branching. Low-density polyethylene (LDPE) prepared by free radical polymer-
ization has a high degree of short- and long-chain branching, which means that the chains do not
pack into the crystal structure as well. High-density polyethylene (HDPE) produced by chromium/
silica catalysts, Ziegler-Natta catalysts, or metallocene catalysts has a low degree of branching
giving it stronger intermolecular forces and tensile strength.
Structures of end groups of a polymer chain are usually not specified because they have little
effect on bulk properties of the polymer and often they are not known. This statement fails in the case
of certain macromolecules such as hyper-branched polymers for which the properties may be
critically dependent on end groups. Introduction of different functional groups at a- and
o-terminals of a polymer molecule can be achieved by the recent development of polymerization
chemistry.

CH2 CH2 CH2 CH2

n
LDPE

CH2 CH
CH2
CH2

HDPE

Fig. 2 Various structures of polyethylene

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Encyclopedia of Polymeric Nanomaterials
DOI 10.1007/978-3-642-36199-9_237-1
# Springer-Verlag Berlin Heidelberg 2014

Fig. 3 Classification of polymerization methods

Polymerization Method
Most polymerization reactions fall into two large classes, chain-growth and step-growth polymer-
izations (Fig. 3). In a chain-growth process, a macromolecule is formed rapidly from monomers via
four stages, i.e., initiation, propagation, chain transfer, and termination. A chain-growth polymer-
ization is further classified into addition polymerization and ring-opening polymerization. Unsatu-
rated compounds and cyclic rings are used for the former and latter polymerizations, respectively.
Addition polymerization of vinyl monomers is called vinyl polymerization. In addition to polymer-
ization, a macromolecule is formed rapidly from monomers via a highly reactive intermediate such
as a free radical, an ion, or a transition metal alkyl complex, which are classified as radical, ionic, and
coordination polymerizations, respectively. In a free radical polymerization, high molecular weight
polymers are initially formed and the molecular weights are independent of the rate of reaction. Ionic
polymerization involves anionic and cationic polymerizations dependent on ionic species at their
propagating ends.
A step-growth polymerization involves slow reactions of two monomers to form dimer, dimer and
monomer to form trimer, two dimers to form tetramer, and so on in all possible combinations until
macromolecules are formed and are classified into polycondensation and polyaddition. 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 %).

Control of Polymer Structure

A special case of chain-growth polymerization leads to living polymerization or controlled poly-
merization, where the ability of a growing polymer chain to terminate and transfer is removed. The
polymer chains grow at a more constant rate than seen in traditional chain-growth polymerization. If
the rate of initiation is also much larger than the rate of propagation, molecular weight distribution is
very narrow (Mw/Mn ~ 1). Living polymerization is a popular method for synthesizing block
copolymers since a polymer can be synthesized in stages, each stage containing a different
monomer. Additional advantages are predetermined molecular weight and control over end groups.

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Encyclopedia of Polymeric Nanomaterials
DOI 10.1007/978-3-642-36199-9_237-1
# Springer-Verlag Berlin Heidelberg 2014

A polymer having pseudochiral carbon atoms in its main chain is isotactic if adjacent centers are
related as in a meso compound, syndiotactic if adjacent centers are related as in a (d,l) compound,
and atactic if stereochemically random. Most polymers made by free radical polymerization of vinyl
monomers are atactic. The development of coordination polymerization initiated by Ziegler-Natta
catalysts and anionic polymerization has most successfully provided stereoregular polymers.

Characteristic of Polymerization
Each polymerization method has advantage as well as disadvantage in comparison with other
methods. Initiation and propagation stages of ionic polymerization highly depend on the polarity
and coordination ability of solvents, in contrast to those of radical polymerization. End groups in
living anionic polymerization are used as highly reactive nucleophiles for a variety of organic
reactions to introduce functional groups such as carboxylic acid and hydroxyl groups. Vinyl ether
derivatives are only polymerized by cationic polymerization. Ring-opening polymerization can
produce heteroatom-containing main chain polymers such as poly(ethylene oxide). Olefins, which
are hardly polymerized by other methods, can be polymerized by coordination polymerization. Most
engineering polymers are obtained by polycondensation or polyaddition. Recent developments of
polymer synthetic chemistry have overcome some of the disadvantages of each polymerization
method, expected to create useful materials for many industrial fields.

Related Entries
▶ Block Copolymers (Fundamental)
▶ Polymer Structures (Overview)
▶ Polymerization Reactions (Overview)

References
1. Roberts RM (1989) Serendipity. John Wiley & Sons, Inc., New York
2. Ravve A (2012) Principles of polymer chemistry, 3nd edn. Springer New York Heidelberg
Dordrecht, London

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