Wardatul H.

1 PREAMBLE

The aim of this chapter is to introduce and summarize the work on polymer nomenclature
which has emanated, firstly, from the Commission on Macromolecular Nomenclature of the
IUPAC Macromolecular Division and, latterly, from the Sub-Committee on Polymer
Terminology of the IUPAC Macromolecular (now Polymer) Division, jointly with the
IUPAC Chemical Nomenclature and Structure Representation Division. The Commission on
Macromolecular Nomenclature is henceforth denoted as ‘the Commission’. Two systems of
polymer nomenclature have been introduced – the source-based and the structure-based. The
latter cannot be used for all types of macromolecule, e.g., statistical copolymer molecules and
polymer networks. IUPAC expresses no strong preference for the use of structure-based
nomenclature versussource-based nomenclature, but for certain purposes one system of
naming may be preferred to the other. .

1.1 The Principles of Source-Based Nomenclature

Traditionally, a polymer has been named by attaching the prefix ‘poly’to the name of the real
or assumed monomer (the ‘source’) from which it is derived. Thus, ‘polystyrene’ is the name
of the polymer made from styrene. Whenthe name of the monomer comprises two or more
words, parentheses should be used [1], as in poly(vinyl acetate), poly(methyl methacrylate),
etc. Failure to use parenthesescan lead to ambiguity. For example, ‘polychlorostyrene’ could
be the name of either a polychlorinated (monomeric) styrene or of a polymer derived from
chlorostyrene; similarly, ‘polyethylene oxide’ could refer to the polymer 1, the polymer 2or
the macrocycle 3.

NOMENCLATURE

These problems are easily overcome with parentheses: names such as ‘poly(chlorostyrene)’
and ‘poly(ethylene oxide)’ clearly indicate the part of the name to which the prefix ‘poly’
refers. However, the omission of parentheses is, unfortunately, still common in the literature.
The principal deficiency of source-based nomenclature is thatthe chemical structure of the
monomeric unit in a polymer is not identical with that of the monomer, e.g., –CHX–CH2–
versus CHX=CH2. The structure of the constitutional repeating unit (CRU) may also not be
clearly identified in this scheme; for example, the name ‘polyacrylaldehyde’ does not indicate
whether (i) the vinyl group or (ii) the aldehyde group was the locus of polymerization.

Depending on the polymerization conditions, different types of polymerization can take place
with many other monomers. Furthermore, a name such as poly(vinyl alcohol) refers to a
hypothetical source, since this polymer is actually obtained by hydrolysis of poly (vinyl
acetate). Despite these serious deficiencies, source-based nomenclature is still firmly
entrenched in the scientific literature. It originated at a time when polymer science was less
developed and the structures of most polymers were ill-defined. The significant advances
made during the last 50 years in the structure determination of polymers are gradually
shifting the emphasis of polymer nomenclature away from starting materials and toward the
structure of the synthesized macromolecules.

1.2 The Principles of Structure-Based Nomenclature

Structure-based nomenclature is based on a method of naming the sequence of constitutional

or structural units that represent the repeating pattern of the structure of a typical
macromolecule in a polymer. The name bears no direct relation to the structure of the
(co)monomer(s) used to synthesize the polymer.

2 IUPAC NOMENCLATURE

2.1 Source-Based Nomenclature

2.1.1 Homopolymers

Although source-based names are usually simpler than structure-based names, historically the
Commission has not systematicallyrecommended source-based names for homopolymers
because they considered that structure-based names were more appropriate for scientific
communications [1]. This rationale was based upon two specific points.

(1) A homopolymer that can be represented by a source-based name can usually be given a
completely unambiguous structure-based representation, and such a representation should
therefore be ideally accompanied by a structure-based name. A source-based name was
therefore deemed redundant in these cases.

(2) There are cases in which the simplicity of source-based nomenclature leads to ambiguous
names for homopolymers. Two examples illustrate this point.

(i) A source-based name such as poly(buta-1,3-diene) or polybutadiene does not indicate

whether the structure contains 1,2, 1,4-cisor 1,4-trans units.

(ii) The polyacrylaldehyde example cited in Section 1.1. Despite the Commission’s long-
standing position, the scientific community has continued to use source-based nomenclature
for homopolymers such as polystyrene and poly(vinyl acetate) because of their simplicity,
convenience and obvious relationship with the monomers from which the homopolymers are
prepared. The Commission therefore decided to recommend source-based nomenclature as an
alternative official nomenclature for homopolymers in a 2001 publication [2]. Consequently,
both source-based and structure-based names are now available for most polymers. The
names of monomers in the source-based names may be traditional or semi-systematic, if well
established by usage, and not necessarily only those retained in the 1993 A Guide to IUPAC
Nomenclature of Organic Compounds[3].

The broad principle is to write the source-based name of a homopolymer by combining the
prefix ‘poly’ with the name of the monomer. When the latter consists of more than one word,
or any ambiguity is anticipated, the name of the monomer is parenthesized. The same
publication [2] recommended a generic source-based nomenclature, which comprises the
optional addition of a polymer class name to the source-based name of the polymer. The
addition is recommended when it is necessary to avoid ambiguity or to add clarification.

Example: the source-based name ‘poly(vinyloxirane)’ is ambiguous; ambiguity about the

structure is removed by writing either ‘polyalkylene:vinyloxirane’ to accompany the source-
based representation,
or ‘polyether : vinyloxirane’ to accompany the source-based representation,

2.1.2 Copolymers

Copolymers are polymers that are derived from more than one species of monomer.

TABEL

Similarly to homopolymers, source-based nomenclature has been applied to copolymers [4].

The principal problem is to define the kind of arrangement in which various types of
monomeric units are related to each other. Seven types of separate arrangements have been
defined, which are shown in Table 1, where A, B and C represent the names of monomers.

The monomer names are linked either through an italicized qualifier or connective (infix),
such as ‘-co-’, to form the name of the copolymer, as in poly(styrene-co-acrylonitrile). The
order of citation of the monomers is arbitrary. The names of copolymers can further be
modified to indicate various structural features. For example, the chemical nature of end
groups can be specified as α-X-ω-Y-polyA-blockpolyB, as in α-butyl-ω-carboxy-polystyrene-
block-polybutadiene. Subscripts placed immediately after the formula of a monomeric unit or
a block designate the degree of polymerization or repetition. On the other hand, mass and
mole fractions and relative molecular masses, which in most cases are average quantities, are
expressed by placing the corresponding figures after the complete name of the copolymer.
The order of citation is as for the monomeric species in the name. Unknown quantities are
designated by a, b, etc. Table 2 gives some examples.

Table 2. Examples of the IUPAC nomenclature formats for copolymers

The complete document [4] should beconsulted for names of more complex copolymers, e.g.
those having a multiplicity of grafts or having chains radiating from a central atom. The
utility of generic source-based nomenclature [2] can also be illustrated for sourcebased names
of copolymers. As for homopolymers, the addition of a polymer class name is recommended
when it is necessary to avoid ambiguity or to add clarification.

Example: the source-based name poly[(benzene-1,2,4,5-tetracarboxylic 1,2:4,5-dianhydride)-

alt-(4,4'-oxydianiline)] is ambiguous; ambiguity about the structure is

removed by writing poly(amide-acid):[(benzene-1,2,4,5-tetracarboxylic 1,2:4,5-dianhydride)-

alt-(4,4'-oxydianiline)] to accompanythe graphical structure-based representation

and polyimide:[(benzene-1,2,4,5-tetracarboxylic 1,2:4,5-dianhydride)-alt-(4,4'-oxydianiline)]

to accompany the graphical structure-based representation

In 1997, the principles of source-based nomenclature were extended to non-linear

macromolecules and macromolecular assemblies [5], which are classified according to the
following terms: cyclic; branched (long- and short-branched); micronetwork; network; blend;
semi-interpenetrating polymer network; interpenetrating polymer network; and polymer—
polymer complex. The range of italicized qualifiers, listed as connectives in

Table 1 for copolymers, was extended by addition of new qualifiers such as ‘blend’,

‘comb’, ‘star’ or ‘net’. Table 3 lists the new qualifiers, together with examples of their use.
Quantitative characteristics of a macromolecule or an assembly of macromolecules, such as
mass and mole fractions or percentages as well as the degrees of polymerization and relative
molecular masses, may be expressed by placing corresponding figures after the complete
name. The complete document [5] should be consulted for details and more examples.
2.2 Structure-Based Nomenclature

2.2.1 Regular Single-Strand Organic Polymers

For organic polymers that are regular (i.e. haveonly one species of constitutional repeating
unit (CRU) in a single sequential arrangement) and comprise only single strands, the IUPAC
has promulgated a structure-based system of naming polymers [1]. The system consists of
naming a polymer as ‘poly(constitutional repeating unit)’, wherein the repeating unit is
named as a divalent organic substituent according to the usual nomenclature rules for organic
chemistry. It is important to note that, in structure-based nomenclature, the name of the
constitutional repeating unit has no direct relationship to the source from which the unit was
prepared. The name is simply that of the identifiable constitutional repeating unit in the
polymer, and locants for unsaturation, substituents, etc are dictated by the structure of the
unit. The steps involved in naming the CRU are: (1) identification of the unit (taking into
account the kinds of atoms in the main chain and the location of substituents); (2) orientation
of the unit; and (3) naming of the unit. The CRUs