S E C T I O N

R U L E S

N o m e n c l a t u r e

W . V. Metanomski Chemical Abstracts Service, Columbus, Ohio, USA

A. Introduction B. IUPAC Recommendations 1. Source-Based Nomenclature 1.1. Homopolymers 1.2. Copolymers 1.3. Nonlinear Macromolecules & Macromolecular Assemblies 2. Structure-Based Nomenclature 2.1. Regular Single-Strand Organic Polymers 2.2. Regular Double-Strand Organic Polymers 2.3. Regular Single-Strand Inorganic and Coordination Polymers 2.4. Regular Quasi-Single-Strand Coordination Polymers 2.5. Irregular Single-Strand Organic Polymers C. Use of Common and Semisystematic Names D. Chemical Abstracts (CA) Index Names E. Polymer Class Names F. References A. INTRODUCTION

1-1 1-1 I-2 I-2 I-2 I-3 I-3 I-6 I-6 I-7 I-7 I-8 I-8 1-11 1-12

Macromolecular (polymer) nomenclature has an almost 50-year history. As early as 1949 there existed a Subcommission on Nomenclature within the International Union of Pure and Applied Chemistry (IUPAC) under the chairmanship of Maurice L. Huggins. The Subcommission was part of the IUPAC Commission on Macromolecules, chaired then by Herman F. Mark. Other notable pioneers in polymer science, Jan Joseph Hermans, Otto Kratky, Harry W. Melville, and George J. Smets, were members of the Commission. The Subcommission produced its first official report in 1952. It recognized then, what is just as true today, that the practice in the field of small molecules of providing rigorous definitions is impractical for polymers. The latter consist of molecules not necessarily exactly of the same size, chemical composition, or structure. The differences result from the presence of end groups, branches, variation in orientation of monomeric units, and irregularity in the sequence of different types of units. The American Chemical Society (ACS) Division of Polymer Chemistry established its Nomenclature Commit-

tee in 1963 to try to unify earlier attempts to name polymers in some coherent way. Their first major project resulted in a structure-based nomenclature for regular linear polymers, first published in ACS Polymer Preprints in 1967, adopted by Chemical Abstracts in 1968, and incorporated in IUPAC recommendations in 1975 [I]. When the IUPAC Commission on Macromolecules was elevated to become the IUPAC Division of Macromolecular Chemistry, the latter in turn established its Commission on Macromolecular Nomenclature in 1968. The Commission in the course of its nearly 30 years of existence produced a series of major documents that have shaped modern nomenclature and terminology of polymer science. The recommendations are being published in the IUPAC official journal, Pure and Applied Chemistry, and occasionally are republished in the form of a "Compendium" which groups all the currently valid documents in a single volume. The Commission published its "Compendium of Macromolecular Nomenclature" in 1991 [2]. The book, which IUPAC has designated the "Purple Book", in analogy to other IUPAC books ("Blue" - organic, "Red" - inorganic, "Orange" - analytical, "Green"- physical, and "Gold" - overall chemistry), has the two most basic macromolecular nomenclature recommendations: "nomenclature of regular single-strand organic polymers" and "source-based nomenclature for copolymers". In more recent years, the Commission extended that basic nomenclature to double-strand (ladder and spiro) organic polymers, irregular and crosslinked polymers, and polymer blends and interpenetrating networks. In this article, the basic structure-based and source-based nomenclature of polymers is explained and illustrated in some detail. The continuing use of common and semisystematic nomenclature with reference to specific tables in this Handbook is highlighted. The current Chemical Abstracts (CA) index names [3] are compared and contrasted with the IUPAC practice and typical names employed in the polymer journals and textbooks. B. IUPAC RECOMMENDATIONS

Since polymers, unlike low-molecular-weight compounds, have no uniform structure and are mixtures of macromolecules of different length and different structural

arrangement, their graphical representation and their names require a special approach. Often enough, the structure of the polymer has not been sufficiently characterized and the researcher cannot draw its chemical structure. Consequently, no name of the polymer reflecting its structure is possible. A polymerization reaction for a polymer formed from a monomer such as vinyl chloride can schematically be represented by

polybutadiene polyethylene poly(methyl methacrylate) poly(methyl vinyl ether) polystyrene poly(tetrafluoroethylene) poly(vinyl alcohol) poly(vinyl acetate) poly(vinyl chloride) poly(vinylidene dichloride) Parentheses are used when the name of the monomer consists of two or more words, and when the monomer has substituents. These are all olefinic type reactants, from which two carbon atoms originally linked by a double bond form a bivalent group:

That shows an idealized product. In fact, however, the polymer consists of long-chains of various lengths. The repeating units, - C H 2 - C H C l - , are not necessarily all uniquely oriented and joined in a regular fashion as shown in the idealized structure above. In addition to "head-totail" links

other links such as "head-to-head"

and "tail-to-tail"

can occur, and the exact sequence of all these repeating units usually is not known. This becomes even more complicated when a copolymer is derived from more than one monomer, such as styrene and methyl acrylate, which contribute two constitutional or monomeric units:

where R and R [ represent a hydrogen atom or a substituent group. Many of these are joined, in turn, to each other but their exact orientation or sequence is seldom known. On the other hand, different polymers derived from a single monomer and having identical constitutional units can still be differentiated by additional information, such as average molecular weight and other chemical and physical characteristics. 1.2. Copolymers For copolymers, the names of monomers are cited after the prefix "poly". In addition, an italicized connective (infix) is placed between the names of monomers to denote the kind of sequential arrangement by which the constitutional (monomeric) units, derived from each monomer, are related in the structure [4]. Seven types of sequence arrangements are listed with their corresponding connectives:

They can combine into a polymeric chain, resulting in many types such as unspecified, statistical, random, alternating, periodic, block, or graft copolymers. Because the exact structure of the polymer is not always known, two systems of naming polymers exist: source-based nomenclature, structure-based nomenclature. 1. Source-Based Nomenclature

Type

Connective -co-stat-raft-alt-per-block-graft-

1.1. Homopolymers Homopolymers are derived from only one species of monomer, which may be the actual starting reactant (or source), or be a hypothetical monomer if the homopolymer is formed by a modification of another homopolymer. The name of the polymer is formed by attaching the prefix "poly" to the name of the actual or assumed monomer, or the starting reactant (source), from which the polymer is derived. Examples: poly (acrylic acid) polyacrylonitrile

unknown or unspecified statistical (obeying known statistical laws) random (obeying Bernoullian distribution) alternating (for two monomeric units) periodic (ordered sequence of more than two) block (linear arrangement of blocks) graft (side blocks chains connected to main chain)

Examples:

poly[styrene-C(?-(methyl methacrylate)! poly^tyrene-statf-acrylonitrile-statf-butadiene) poly[ethylene-ran-(vinyl acetate)] poly[(ethylene glycol)-tf/r-(terephthalic acid)] poly[formaldehyde-/?er-(ethylene oxide)-per(ethylene oxide)] polystyrene-&/oc&-polybutadiene polybutadiene-gra/f-polystyrene

The names of the monomers are those common or semisystematic names that are encountered most often in the literature of polymer science. The order of citation of monomers in copolymer names is arbitrary. An equally acceptable alternative scheme for naming copolymers utilizes the prefix "copoly", followed by citation of the names of the monomers, separated by an oblique stroke (a solidus). Parentheses are not needed to enclose monomer names consisting of two or more words. Examples: copoly(styrene/methyl methacrylate) j"tatf-copoly(styrene/acrylonitrile/butadiene) ran-copoly(ethylene/vinyl acetate) a/f-copoly(ethylene glycol/terephthalic acid) per-copoly(formaldehyde/ethyleneoxide/ethylene oxide) Wtfc/:-copoly(styrene-butadiene) gra/-copoly(butadiene-styrene)

the constituent macromolecules with an italicized connective between them. Examples: poly styrene-com>-poly aery lonitrile com&-poly(styrene~statf-acrylonitrile) poly styrene-comZ?- [poly acrylonitrile; poly(methyl methacrylate)] 4-sfar-polystyrene star-(po\yA-block-polyB-block-polyC) star-(polyA; polyB; polyC) star-(polyacrylonitrile; polystyrene) (M1 100000:20000) fte-polystyrene--divinylbenzene n^-poly[styrene-<3/Kmaleic anhydride)]^-(ethylene glycol) polystyrene-Weftd-poly(2,6-dimethylphenol) poly(methyl methacrylate)-We?i(i-poly(tt-butyl acrylate) (net-polystyrene)-sipn-poly(vinyl chloride) [net-poly(styrenQ-stat-butSidiene]-ipn-[netpoly(ethyl acrylate)

1.3. Nonlinear Macromolecules and Macromolecular Assemblies Most recently, the source-based nomenclature has been extended for non-linear macromolecules and macromolecular assemblies [5], The non-linear macromolecules comprise branched, graft, comb, star, cyclic, and network macromolecules. The macromolecular assemblies comprise polymer blends, interpenetrating polymer networks, and polymer-polymer complexes. The following italicized qualifiers can be used as both prefixes (e.g., blend-, net-) and infixes (connectives) (e.g., -blend-, -net-) to designate the skeletal structure of nonlinear macromolecules or macromolecular assemblies:

2.

Structure-Based Nomenclature

2.1. Regular Single-Strand Organic Polymers For regular organic polymers which have only one species of constitutional repeating unit (CRU) in a single sequential arrangement and consist of single strands only, the name is poly(constitutional repeating unit), wherein the repeating group is named as a bivalent organic group according to the IUPAC nomenclature rules for organic compounds [I]. Each such repeating group can consists of simple or substituted subunits such as: methylene ethylene vinylene hexane-l,6-diyl 1-chloroethylene 1 -oxopropane-1,3-diyl adipoyl 1,4-phenylene cyclohexane-1,4-diyl oxy thio sulfonyl imino methylimino hydrazo piperidine-1,4-diyl silanediyl dimethylsilanediyl Before the total constitutional repeating unit (CRU) can be given a unique name, a single preferred CRU must be selected. References page 1-12

Type cyclic branched, unspecified short-chain-branched long-chain-branched branched with branch point of functionality / comb star star with / arms network crosslink polymer blend interpenetrating polymer network semi-interpenetrating polymer network polymer-polymer complex

Connective cyclo branch sh-branch l-branch f-branch comb star f-star net t (Greek iota) blend ipn sipn compl

In naming non-linear homopolymer molecules, the italicized prefix for the skeletal structure of the macromolecule is placed before the source-based name of the constituent linear chain. Assemblies of macromolecules held together by noncovalent bonds are named by a combination of the names of

For instance, in a polymer such as

d. for carbon-only acyclic chains, seniority is determined first by length, then by the number of substituents, by the ascending order of locants, and, finally, by the alphabetical order of the names of the substituent groups. In all cases, the basic seniority rules apply only to those atoms or groups of atoms that are in the main chain. The kinds of substituents on the main chain (whether acyclic carbon-only groups, or hetero-atom-containing groups, or any ring systems) do not affect the selection of the CRU, unless identical basic subunits in the chain have to be further differentiated by the number of substituents and their alphabetical order, but not by the type of the substituent. If completely identical subunits are separated by other subunits, the direction of citation is determined by the shorter part between them. The preferred CRU is the one beginning with the subunit of highest seniority. To establish direction, one proceeds from this subunit to the neighboring subunit of the same or next in seniority. In the example of a poly(chloroethylene oxide), shown above, where a regularly repeating structure has been assumed, the subunit of the highest seniority is the oxygen atom and the subunit next in seniority is a substituted - C H 2 - C H 2 - . The substituted subunit, - C H C l - C H 2 - , is oriented in such a way that the substituent, chlorine atom, is assigned the lowest locant (1 rather than 2). The CRU is written to read from left to right. Thus, the preferred CRU is

it is immediately evident that a three-atom group (oxygen, chlorine-substituted methylene group, and methylene group) are being regularly repeated. Yet, the CRU can be identified in at least three ways

To obtain a unique name based on a preferred CRU, several rules have to be applied. Rules have been developed to specify both seniority among subunits, that is, the point at which to begin writing the CRU, and also the direction in which to move along the chain from left to right to reach the end of the chain. The order of seniority among the types of bivalent groups that are parts of the chain of a single-strand polymer is a. heterocycles, e.g., piperidine-l,4-diyl: thiophene-2,5-diyl: b. heteroatomic acyclic groups, e.g., oxy: - O - , sulfonyl: - S O 2 - , imino: - N H c. carbocycles, e.g., 1,4-phenylene: cyclobutane-1,3-diyl: d. carbon-containing acyclic groups, e.g., 1-chloroethylene: - C H C l - C H 2 propane-1,3-diyl: - C H 2 - C H 2 - C H 2 Within each structural type, the seniority is established by further criteria: for heterocycles, a ring system containing nitrogen is senior to a system containing a hetero atom other than nitrogen, with further descending order of seniority governed by the greatest number of rings in the ring system, the largest individual ring in the ring system, the largest number of hetero atoms, and the greatest variety of hetero atoms; b. for heteroatomic acyclic chains, oxygen is senior to sulfur, sulfur to nitrogen, nitrogen to phosphorus, phosphorus to silicon, silicon to germanium, etc.; c. for carbocycles, a three-ring system is senior to a two-ring system, a two-ring system containing two 6-membered rings is senior to one containing a 5and a 6-membered rings, a fused two-ring system (two atoms common to both rings) is senior to a spiro two-ring system (one atom in common), and an unsaturated ring is senior to a saturated ring of the same size; a.

and the polymer

is named poly [oxy (1 -chloroethylene)] The second example:

poly [(methylimino)methyleneimino-1,3-phenylene] illustrates a polymer whose CRU starts with a substituted nitrogen atom and proceeds through the shortest path to the unsubstituted nitrogen atom and then through a carbocycle. The chemical structure of the CRU is enclosed in parentheses or brackets. While dashes representing chemical bonds may be omitted within the formula unless necessary for clarity, at the ends of the CRU, dashes must be shown. They are drawn across the enclosing marks.

The third example:

symbol a denoting the left-hand end group and the symbol co denoting the other end group. Example:

poly(pyridine-3,5-diylcarbonyloxymethylene) shows a polymer, whose CRU starts with a heterocycle and then proceeds through a substituted carbon atom to a hetero atom. If the end groups of the chain are known, they may be specified by adding prefixes to the polymer name, with the

a-(trichloromethyl)-co-chloropoly (1,4-phenylenemethylene) The following table compares and contrasts structurebased and source-based names of some common polymers.

Structure

Structure-based name Poly(methylene) Poly(propylene) Poly (1,1 -dimethylethylene) Poly (1 -methyl-1 -butenylene) Poly (1 -phenylethylene)

Source-based or trivial name Polyethylene Polypropene Polyisobutylene Polyisoprene Polystyrene

PoIy(I -chloroethylene) Poly (1 -cyanoethylene) PoIy(I-acetoxyethylene) PoIy(1,1-difluoroethylene) Poly(difluoromethylene) Poly[(2-propyl-1,3-dioxane-4,6-diyl)methylene]

Poly(vinyl chloride) Poly aery lonitrile Poly(vinyl acetate) Poly(vinylidene fluoride) Polytetrafluoroethylene Poly(vinyl butyral)

Poly[ 1 -(methoxycarbonyl)-1 -methylethylene] Poly(oxyethylene) Poly(oxy-1,4-phenylene)

Poly(methyl methacrylate) Poly(ethylene oxide) Poly(phenylene oxide)

Poly[imino(l-oxohexane-1,6-diyl)]

Poly(e-caprolactam)

Poly(oxyethyleneoxyterephthaloyl)

Poly(ethylene terephthalate)

Poly(iminoadipoyliminohexamethylene) Poly[(2,5-dioxotetrahydrofuran-3,4-diyl)( 1 -phenylethylene)]

Poly(hexamethylenediamine-a/?-adipic acid) or poly(hexamethylene adipamide) Poly(maleic anhydride-a/r-styrene)

References page 1-12

2.2. Regular Double-Strand Organic Polymers In a double-strand polymer, the macromolecules consist of an uninterrupted sequence of rings with adjacent rings having two or more atoms in common (a ladder polymer) or one atom in common (a spiro polymer). As for a single-strand polymer, a single preferred constitutional repeating unit (CRU) must be selected in order to obtain a unique name [6]. The CRU is usually a tetravalent group denoting attachment to four atoms and is named according to the usual rules of organic nomenclature. Again, the name of the polymer is in the form of poly(constitutional repeating unit) Since the polymer has a sequence of rings, in order to identify a preferred CRU, the rings must be broken by observing the following criteria in decreasing order of priority: a. minimize the number of free valences in the CRU, b. maximize the number of most preferred hetero atoms in the ring system, c. retain the most preferred ring system, and d. choose the longest chain for acyclic CRU. Further decisions are based on the seniority of ring systems (indicated in the preceding section), on the orientation of the CRU to give the lowest free valence locant at the lower left of the structural diagram, and on placing the acyclic subunits, if any, on the right side of the ring system within the CRU. For a polymer consisting of adjacent 6-membered saturated carbon rings:

common at each junction:

the name based on the preferred CRU is

poly(l,4-dithiin-2,3:5,6-tetrayl-5,6-dicarbonyl) Here, by applying the seniority of the rings system, the heterocycle was left intact, but the carbocycle was broken. That left two bivalent acyclic subunits (carbonyl groups), which according to the rule, have been placed on the right side of the cyclic subunit, with attachments as in the original polymer. Another, still more complex ladder polymer, derived from the polycondensation of 1,4,5,8-naphthalenetetracarboxylic dianhydride with 1,2,4,5-benzenetetramine:

poly[(7-oxo-7//,10//-benz[<ie]imidazo[4/,5/: 5,6]benzimidazo [2,l-a]isoquinoline-3,4:10,ll-tetrayl)-10-carbonyl] illustrates a six-ring system with four free valences oriented in such a way that the lowest free valence locant is at lower left. It is followed within the total CRU by an acyclic group at the upper right side of the diagram. For a polymer consisting of regularly repeating adjacent cyclohexane and 1,3-dioxane rings in a spiro sequence (one atom in common at each junction):

the name of the preferred CRU, which in this case is an acyclic chain of four carbon atoms with four free valences at each atom (the lowest at the lower left), is

poly (butane-1,4: 3,2-tetrayl) The free valence locants are always placed just in front of the corresponding ending of the tetravalent unit and are cited in the order lower-left, upper-left: upper-right, lower-right that is, in a clockwise direction, the left locants being separated from the right locants by a colon. For a more complex ladder polymer consisting of an alternating sequence of 6-membered sulfur-containing rings and keto-group containing carbocycles, with two atoms in

the preferred CRU and the name are:

poly(2,4,8,10-tetraoxaspiro[5.5]undecane-3,3:9,9-tetrayl-9,9-diethylene)

2.3. Regular Single-Strand Inorganic and Coordination Polymers The names of inorganic and coordination polymers are based on the fundamentals developed for organic polymers [7]. As in the nomenclature of organic polymers, these rules apply to structural representations

which may at times be idealized and do not take into account irregularities, chain imperfections, or random branching. A constitutional repeating unit (CRU) is selected and named. However, because of the basic difference between the organic and inorganic nomenclature, the subunits of the CRU are not named as bivalent groups, but as inorganic or coordination groups indicating covalent and/or coordinate bonding. The name of the polymer is the name of the CRU prefixed by the term "poly", "catena", or other structural indicator. In order to arrive at the preferred CRU, seniorities of the constitutent subunits are considered as well as the preferred direction for the sequential citation. The constituent subunit of the highest seniority must contain one or more central atoms; bridging groups between central atoms in the backbone of the polymer are of lower seniority. This is consistent with the principle of coordination nomenclature which puts the emphasis on the coordination center. Examples of homoatomic backbones are

2.4. Regular Quasi-Single-Strand Coordination Polymers In a regular quasi-single-strand coordination polymer, the preferred CRU has one terminal constituent subunit connected through a single atom to the next CRU [7]. Such polymers are named as single-strand coordination polymers:

catena-poly [palladiumdi-u-chloro]

catena-polyfsilicondi-u-thio]

catena-poly[platinum(ubromo-u-chloro)]

catena-poly [titaniumtri-u-chloro]

catena-poly [dimethyltin]

caterca-poly[(difluorosilicon) (dimethylsilicon)]

More common coordination polymers consist of a mononuclear central atom with a bridging ligand. The CRU of such a polymer cites the central atom first, which is prefixed by its associated non-bridging ligands, followed in turn by the name of the bridging ligand prefixed by the Greek letter \i:

2.5. Irregular Single-Strand Organic Polymers Irregular polymers are named by placing the prefix "poly" before the structure-based names of the constitutional units, collectively enclosed in parentheses or brackets, with the individual constitutional units separated by an oblique stroke (a solidus) [8]. The stroke indicates the irregular or unknown sequential arrangement of these units. The dashes at each end of the formula are drawn fully inside the enclosing marks to denote that these are not necessarily terminal bonds of the macromolecule. For instance, a partially hydrolyzed poly(vinyl acetate) containing units:

is represented graphically and named:

catena-poly [(amminechlorozinc)-u-chloro]

catena-pory[(dihydroboron)-ju-(dimethylamido)] poly( 1 -acetoxyethylene/1 -hydroxyethylene)

Multiple bridging ligands between the pair of central atoms are cited in alphabetic order. Italicized element symbols indicating the coordinating atoms in bridging ligands are cited in the order of direction of the CRU and are separated by a colon:

A copolymer of vinyl chloride and styrene joined head-totail is

poly (1 -chloroethy lene/1 -pheny lethylene) A chlorinated polyethylene consisting of units

catena-poly [copper-[|i-chloro-bis-u-(diethyl S')] -copper- u-chloro]

disulfide-S: References page 1-12

is shown and named as

poly(chloromethylene/dichloromethylene/methylene) C. USE OF COMMON AND SEMISYSTEMATIC NAMES

The main purpose of chemical nomenclature is to identify a chemical species by means of written or spoken words for a useful communication among chemists. A systematic nomenclature arose from the need to provide a relationship between the structure and the name. In other words, the reader should be able to deduce and identify the structure from the name. Traditional names, however, not necessarily based on structures, have been widely used for many common compounds. These are the so-called common, trivial, or semisystematic names, which are satisfactory for communication within a given special chemical field. It was earlier stated that in the macromolecular nomenclature IUPAC is recommending the use of common and semisystematic names for monomers in the sourcebased polymer names. The structure-based names, on the other hand, are more related to the structural characteristic of the polymers. But even there, IUPAC allows for a limited number of common names for such substituent groups as "allyl" and "vinyl", and for bivalent groups such as "adipoyl" and "terephthaloyl". The authors in this Handbook for the most part are using the IUPAC-recommended names, or very close variants thereof. On the other hand, in some compilations such as "Crystallographic Data for Various Polymers" (in Section VI), the author provides an excellent introduction and explanation of the names used. For some structure-based names, reflecting constitutional repeating units (CRU), especially for those with a center of symmetry, the naming of linking bivalent groups begins with the central subunit and proceeds in both directions. The IUPAC method selects the most senior bivalent group and proceeds naming from left to right. Examples:

In no case, there is any misunderstanding in either case as to which structure is associated with each name. Abbreviations and acronyms are also extensively used in the chemical literature for monomers, polymers, as well as for additives, modifiers, and fillers. Their extensive list is provided in Section VIII of this Handbook. As is clearly stated there, the same abbreviation is often used for different monomers and polymers, and the same polymer may have different abbreviations or acronyms. Examples: 1. DPP 2. PVA 3. trioctyl phosphate 4. polyacrylonitrile

diphenyl phthalate dipropyl phthalate poly(vinyl alcohol) poly(vinyl acetate) TOF TOP PAC PAN

The IUPAC policy [9] on the use of abbreviations in the chemical literature states that there are great advantages in defining all abbreviations in a single conspicuous place in each paper, preferably near the beginning of the paper in a single list. An alternative is to define each abbreviation fully the first time it appears in the text. No abbreviations should be used in the titles of publications. A chapter of this Handbook contains a set of abbreviations recognized by international organizations. D. CHEMICAL ABSTRACTS (CA) INDEX NAMES

Chemical Abstracts Service (CAS), the publisher of printed Chemical Abstracts (CA) and corresponding products and services in microform, online databases, CD-ROM, and World Wide Web also names the polymers, selected for inclusion in the CAS Chemical Registry System and in the CA Chemical Substance Indexes, in two ways: in terms of the component monomer(s) from which they are prepared b. in terms of the final structure of the resulting polymer. There are definitive rules that govern when each type of structure is recorded and named [3], The primary, comprehensive representation of polymers by CAS is by citation of the component monomer(s) because, in many cases, the structure of the final polymer is either not known or is not described in sufficient detail by the author. When the polymer structure is well documented by the author or can be confidently assumed, because one and only one structure is chemically possible, then a supplementary representation with a corresponding systematic name is added to the CAS Registry System and included in the printed indexes and online files. a.

Handbook name: poly(4,4'-sulfonyldiphenylene carbonate) IUPAC name: poly(oxycarbonyloxy-l,4-phenylenesulfonyl-1,4-phenylene) 2.

Handbook name: poly (oxy die thy lene succinate) IUPAC name: poly(oxyethyleneoxyethyleneoxysuccinyl)

The chemical nomenclature used by CAS has developed in parallel, and generally in accordance, with the rules and recommendations published by IUPAC. However, their rules of systematic nomenclature do not necessarily lead to a unique name for each compound, but do lead to an unambiguous one. This causes no difficulty in normal scientific communication, but is unacceptable in a formal, rigidly controlled, alphabetic listing such as the CA Chemical Substance Index. The CA index names must not only be unambiguous, unique, and totally reproducible, but also selected so as to bring the names of structurally related substances into juxtaposition in the alphabetic index. CAS has always recognized that, while a unique name is needed for an index and for substance identification, the use of such invariant name in scientific papers is neither practicable nor desirable. In this section, it is intended to highlight the characteristics of the CA index names for polymers and compare them with some of the typical names used in the scientific community. a. b. IUPAC rules have been adapted to the specific needs of a highly ordered alphabetical index. Most common names were eliminated and exceptional treatment for various classes of substances was discontinued. A single preferred name is determined for each identifiable substance. A strict order of precedence of chemical functions and compound classes is followed to determine the preferred "index heading parent". A total name is "inverted" by citing first the index heading parent (usually, basic skeleton name with a locant and suffix denoting the principal function), followed by the comma of inversion, the substituents, and the modification (derivative of the principal function), e.g., 2-propenoic acid, 2-methyl-, methyl ester

glycolic acid hydroquinone isophthalic acid lactic acid maleic acid maleic anhydride melamine methacrylic acid methyl acrylate phthalic anhydride propylene oxide styrene terephthalic acid vinyl alcohol vinyl chloride vinylidene chloride

acetic acid, hydroxy1,4-benzenediol 1,3-benzenedicarboxylic acid propanoic acid, 2-hydroxy2-butenedioic acid, (Z)2,5-furandione 1,3,5-triazine-2,4,6-triamine 2-propenoic acid, 2-methyl2-propenoic acid, methyl ester 1,3-isobenzofurandione oxirane, methylbenzene, ethenyl1,4-benzenedicarboxylic acid ethenol ethene, chloroethene, 1,1-dichloro-

Similarly, commonly named substituent and multiplying groups have their systematic equivalents in CA Indexes: adipoyl allyl tert-butyl ethylene hexamethylene isopropyl succinyl vinyl vinylene 1,6-dioxo-1,6-hexanediyl 2-propenyl 1,1 -dimethylethyl 1,2-ethanediyl 1,6-hexanediyl 1-methylethyl 1,4-dioxo-1,4-butanediyl ethenyl 1,2-ethenediyl

c. d.

e.

Homopolymers are described by the term "homopolymer" cited in the modification under the monomer name in the index. In the structural diagram derived from the CAS Registry System records, the structure of the monomer is enclosed in parentheses followed by a subscript "x". The corresponding empirical formula is also expressed in a similar way. Examples: 1. Poly (methacrylic acid): (CH 2 =CH-COOH) x CH3 (C 4 H 6 O 2 ), CA name: 2-Propenoic acid, 2-methyl-, homopolymer 2. Polystyrene: (CH2=CH)x C6H5 (C 8 H 8 ), CA name: Benzene, ethenyl-, homopolymer 3. PoIy(11-aminoundecanoic acid): (H 2 N-(CH 2 )Io-COOH), (C 11 H 23 NO 2 ), CA name: Undecanoic acid, 11-amino-, homopolymer References page 1-12

As mentioned above, most common names, including those still sanctioned by IUPAC, have been replaced by fully systematic names. The following is a short list of most common monomers with both common names and CA Index names: Common acrylamide acrylic acid acrylonitrile adipic acid 8-caprolactam 8-caprolactone ethylene glycol ethylene oxide fumaric acid CA Index names (inverted form) 2-propenamide 2-propenoic acid 2-propenamide hexanedioic acid 2//-azepin-2-one, hexahydro2-oxepanone 1,2-ethanediol oxirane 2-butenedioic acid, (E)-

4. Poly (lac tic acid): (CH3-CH-COOH)x OH (C3H6O3)* CA name: Propanoic acid, 2-hydroxy-, homopolymer Copolymers formed from two or more monomers are described by the term "polymer with" (followed by the other monomers in alphabetical order) cited in the modification under each monomer name. In the structural diagram derived from the CAS Registry System records, the structures of monomers, separated by a period or periods, are enclosed in parentheses followed by a subscript ' V . The corresponding empirical formulas are similarly expressed. The descriptors alternating, block, and graft are cited whenever applicable. Examples: 1. Butadiene-vinyl ethyl ether copolymer: (CH2=CH-CH=CH2CH2=CH-O-CH2CH3)X (C4H8OC4H6)Jt (in Formula Index order) CA names: 1,3-Butadiene, polymer with ethoxyethene Ethene, ethoxy-, polymer with 1,3butadiene 2. Isophthalic acid-terephthalic acid-ethylene glycol polyester: (HOOC-m-C6H4-COOHHOOC-p-C6H4-COOHOH-(CH2)2-OH)X (C 8 H 6 O 4 C 8 H 6 O 4 C 2 H 6 O 2 ), CA names: 1,3-Benzenedicarboxylic acid, polymer with 1,4-benzenedicarboxylic acid and 1,2-ethanediol 1,4-Benzenedicarboxylic acid, polymer with 1,3-benzenedicarboxylic acid and 1,2-ethanediol 1,2-Ethanediol, polymer with 1,3-benzenedicarboxylic acid and 1,4-benzenedicarboxylic acid Telomers are named as copolymers with the term "telomer with" cited in the modification under both the monomer (taxogen) and the chain-transfer agent (telogen). In the structural representation, the monomer is enclosed in parentheses with a subscript "*", followed by the telogen structure. The corresponding empirical formula is expressed in the same way. Examples: 1. Vinylpyrrolidone homopolymer terminated with mercaptopropionic acid:

CA names: 2-Pyrrolidinone, 1-ethenyl-, telomer with 3-mercaptopropanoic acid Propanoic acid, 3-mercapto-, telomer with l-ethenyl-2-pyrrolidinone 2. Acrylic acid-vinyl choride copolymer terminated with carbon tetrachloride:
(CH 2 =CH-COOH-CI-CH=CH 2 )X-CCI 4

(C3H4O2C2H3Cl)xCCl4 CA names: 2-Propenoic acid, telomer with chloroethene and tetrachloromethane Ethene, chloro-, telomer with 2-propenoic acid and tetrachloromethane Methane, tetrachloro-, telomer with chloroethene and 2-propenoic acid Structural repeating units (SRU), equivalent to IUPAC constitutional repeating units (CRU), are selected and named for polymers that have well documented regular structure, or can confidently be assumed. Assumptions are made for a. polyamides formed from a dibasic acid (ester or halide) and a diamine; from an amino acid (ester or halide); from a lactam; b. polyesters formed from a dibasic acid (anhydride, ester, or halide) and a dihydric alcohol (phenol); from a hydroxy acid (ester, halide); from a lactone; c. polycarbonates formed from carbonic acid (ester, dihalide) and a dihydric alcohol (phenol); d. polyurethanes formed from a diisocyanate and a dihydric alcohol (phenol). The structural repeating unit is named by citation of one or more multivalent radicals of regular substitutive nomenclature. The selection of the preferred SRU, its orientation, and the construction of the name, proceeding from left to right, follows the same rules as those in the IUPAC recommendations for the CRU. In CA names, however, the names of the radicals are fully systematic, as explained and contrasted above. The empirical formula is enclosed in parentheses followed by a subscript "n". Examples: 1. Nylon 11:

CA name: Poly[imino(l-oxo-l,ll-undecanediyl)] 2. Poly(ethylene adipate):

CA name: Poly[oxy-1,2-ethanediyloxy(1,6-dioxo1,6-hexanediyl)]

3. Poly (ether ether ketone) (PEEK):

CA name: Poly(oxy-1,4-phenyleneoxy-1,4-phenylenecarbonyl-1,4-phenylene) Poly(alkylene glycols) and their ethers and esters are indexed in CA as structural repeating units with the specified end groups, if aplicable. Examples: 1. Poly(ethylene glycol): HfO-CH 2 -CH 2 ^ n OH CA name: Poly(oxy-l,2-ethanediyl), a-hydroco-hydroxy2. Poly(trimethylene glycol) dimethyl ether: CH3 4 0 - C H 2 - C H 2 - C H 2 ^ O - C H 3 CA name: Poly(oxy-1, 3-propanediyl), a-methylco-methoxy3. Poly(tetramethylene glycol) diacrylate: CH2=CH-C(O) 40-CH 2 -CH 2 -CH 2 -CH 2 ^ n 0-C(O)-CH=CH 2 CA name: Poly(oxy-1, 4-butanediyl), a-(l-oxo2-propenyl)-co- [(1 -oxo-2-propenyl)oxy ] E. POLYMER CLASS NAMES In most textbooks, handbooks, encyclopedias, and indexes to polymer nomenclature, information on polymer is grouped under polymer class names. The following is a list of such terms extracted from these sources. Acrylic Polymers Alkyd resins Aminoplasts Coumarone-indene-resins Epoxy resins Fluoropolymers Phenolic resins Polyacetals Polyacetylenes Polyacrylics Polyalkylenes Polyalkenylenes Polyalkynylenes Polyamic acids Polyamides Polyamines Polyanhydrides Polyarylenealkenylenes Polyarylenealkylenes Polyarylenes Polyazomethines

Polybenzimidazoles Polybenzothiazoles Polybenzoxazinones Polybenzoxazoles Polybenzyls Polycarbodiimides Polycarbonates Polycarboranes Polycarbosilanes Polycyanurates Polydienes Polyester-polyurethanes Polyesters Polyetheretherketones Polyether-polyurethanes Polyethers Polyhydrazides Polyimidazoles Polyimides Polyimines Polyisocyanurates Polyketones Polyolefins Polyoxadiazoles Polyoxides Polyoxyalkylenes Polyoxyarylenes Polyoxymethylenes Polyoxyphenylenes Polyphenyls Polyphosphazenes Polypyrroles Polypyrrones Polyquinolines Polyquinoxalines Polysilanes Polysilazanes Polysiloxanes Polysilsesquioxanes Polysulfides Polysulfonamides Polysulfones Polythiazoles Polythioalkylenes Polythioarylenes Polythioethers Polythiomethylenes Polythiophenylenes Polyureas Polyurethanes Polyvinyl acetals Polyvinyl butyrals Polyvinyl formals Vinyl polymers

These classes are not mutually exclusive, some are relatively generic and some more specific. Some of them References page 1-12

could be grouped and arranged in a hierarchy, e.g., Polyacetals Polyvinyl acetals polyvinyl butyrals polyvinyl formals Polyesters polycarbonates Polyethers epoxy resins polyetheretherketones polyoxyalkylenes polyoxymethylenes polyoxyarylenes polyoxyphenylenes

Some are synonymous or near synonymous, e.g., polyalkenylenes and polydienes, polyalkynylenes and polyacetylenes, polyethers and polyoxides, polythioethers and polysulfides. F. REFERENCES 1. IUPAC, "Nomenclature of Regular Single-Strand Organic Polymers (Recommendations 1975)", Pure Appl. Chem. 48, 373 (1976). Reprinted as Chapter 5 in Ref. 2. 2. IUPAC, "Compendium of Macromolecular Nomenclature". W. V. Metanomski, (Ed.), Blackwell Scientific, Oxford, 1991.

3. Chemical Abstracts Service, "CA Index Guide 1997", Appendix IV, "Chemical Substance Index Names", Chemical Abstracts Service, Columbus, Ohio, 1997. 4. IUPAC, "Source-Based Nomenclature for Copolymers (Recommendations 1985)", Pure Appl. Chem. 57, 1427 (1985). Reprinted as Chapter 7 in Ref. 2. 5. IUPAC, "Source-Based Nomenclature for Non-Linear Macromolecules and Macromolecular Assemblies (Recommendations 1997)", Pure Appl. Chem. 69, 2511 (1997). 6. IUPAC, "Nomenclature of Regular Double-Strand (Ladder and Spiro) Organic Polymers (Recommendations 1993)", Pure Appl. Chem. 65, 1561 (1993). 7. IUPAC, "Nomenclature for Regular Single-Strand and Quasi-Single-Strand Inorganic and Coordination Polymers (Recommendations 1984)", Pure Appl. Chem. 57, 149 (1985). Reprinted as Chapter 6 in Ref. 2. 8. IUPAC, "Structure-Based Nomenclature for Irregular Single-Strand Polymers (Recommendations 1994)", Pure Appl. Chem. 66, 873 (1994). 9. IUPAC, "Use of Abbreviations in the Chemical Literature (Recommendations 1979)", Pure Appl. Chem. 52, 2229 (1980).