社団法人高分子学会

Prepared by a Working Group of IUPAC IV.1 Subcommittee of Macromolecular Terminology consisting of

K. Horie (Japan), M. Barón (Argentina), R. B. Fox (USA), J. He (China), M. Hess (Germany), J. Kahovec (Czech Republic), T. Kitayama (Japan), P. Kubisa (Poland), E. Maréchal (France), W. Mormann (Germany), G. Swift (USA), D. Tabak (Brazil), J. Vohlídal (Czech Republic), E. S. Wilks (USA), W. J. Work (USA)

This document has been prepared to present clear concepts and definitions of general and specific terms with regard to reactions of polymers and to functional polymers. The document is divided into three sections. In Section 1, terms relating to reactions involving and specific to polymers are defined. Names of individual chemical reactions, e.g., chloromethylation, are omitted from this document, even for cases where the reactions are important in the field of polymer reactions, because they usually duplicate those already in widespread use and well defined in organic and other areas of chemistry [6]. Sections 2 and 3 deal with the terminology of reactive and functional polymers. The term "functional polymer" has two meanings: (A) a polymer bearing functional groups (such as hydroxy, carboxy, or amino groups) which make the polymer reactive, (B) a polymer performing a specific function for which it is produced and used. The function in the latter case may be either a chemical function such as reactivity or a physical function like electrical conductivity. Polymers bearing reactive functional groups are usually regarded as polymers capable of undergoing chemical reactions. Thus, Section 2 deals with polymers and polymeric materials which undergo various kinds of chemical reactions, i.e., show chemical functions. Section 3 deals with terms relating to polymers and polymeric materials exhibiting some specific physical functions. For definitions of some physical functions, see also Compendium of Chemical Terminology (“Gold Book”) [7].

A functional polymer is defined in Definition 3.6 of the present document as "a polymer that exhibits specified chemical reactivity or has specified physical, biological, pharmacological, or other uses". Thus, several terms concerned with properties or structure of polymers are included in Section 3, whenever they are closely related to some specific functions.

A document on structure-based and source-based polymer class names [8] is in preparation by IUPAC Subcommittee of Macromolecular Terminology. A significant part of Sections 2 and 3 of this recommendation can also be regarded as a glossary of polymer class names based on chemical and physical functions.

A process through which a radiation-induced chemical event initiates a chain reaction that increases the sensitivity to change in some physical properties of a polymeric material.

1. A chemical amplification process is often utilized in lithography of photo-resists with a photo-acid generator or photo-base generator.

2. An example of a chemical amplification process is the transformation of [(tert-butoxycarbonyl)oxy]phenyl groups in polymer chains to hydroxyphenyl groups catalyzed by a photo-generated acid.

3. Photopolymerization and radiation-induced depolymerization may also be regarded as chemical amplification processes.

In the case of polymers, a process by which at least one feature of the chemical constitution of a polymer is changed by chemical reaction(s).

The reversible change in configurational structure, e.g. cis-trans isomerization, is usually excluded from chemical modification.

A reaction involving pairs of polymer chains that results in the formation of small regions in a polymer from which at least four chains emanate. (see Definition 1.59 in [2])

2. A reaction of a reactive chain end of a linear polymer or monomer with an internal reactive site of another linear polymer results in the formation of a branch point, but is not regarded as a crosslinking reaction.

A chemical process of converting a prepolymer or a polymer in a viscous or solid state into a product in which the polymer or prepolymer attains higher molar mass or becomes a network.

2. Physical aging, crystallization, and physical crosslinking are sometimes referred to as "curing" (e.g. in polyamide crystallized by stretching). Use of the term "curing" in these cases is discouraged.

In the case of polymers, a chemical reaction that leads to the formation of one or more new rings in polymer chains.

1. Examples of cyclization along a polymer chain are: (a) cyclization of poly(acrylonitrile), (b) acetalization of poly(vinyl alcohol) with an aldehyde, (c) cyclization of polymers of conjugated dienes such as polyisoprene or polybutadiene.

2. Examples of cyclization of a polymer molecule are: (a) cyclization of poly(dimethylsiloxane), (b) back-biting during ionic polymerizations of heterocyclic monomers.

Chemical changes in a polymeric material that usually result in undesirable changes in in-use properties of the material.

1. In most cases (e.g. in vinyl polymers, polyamides) degradation is accompanied by a decrease in molar mass of the macromolecule. In some cases (e.g. in main-chain aromatic polymers) degradation is accompanied also by crosslinking.

2. Usually degradation results in the loss of, or deterioration in, in-use properties of the material. However in the case of biodegradation, it can result in better in-use properties of polymers (see Definition 3.1).

3. See Definition 16 in [5].

The process of converting a polymer into its monomer or a mixture of monomers.

See Definition 3.25 in [2].

In the case of polymers, introduction of chemical groups into a polymer molecule that exert specific chemical, physical, biological, pharmacological, or other functions.

A polymer reaction in which blocks (see Definition 1.62 in [2]) of one or more types are attached as side chains to a polymer molecule having a constitutional or configurational feature different from that of the attached blocks.

A reaction that results in a chemical exchange between two reactive groups, either between two different molecules, either polymeric or low-molar-mass, or between two non-adjacent sites within the same macromolecule.

A typical interchange reaction that occurs with polyesters is called transesterification.

A chemical reaction that results in breaking of main-chain bonds of a polymer molecule (see Definition 1.34, 3.24 in [2]).

Some main-chain scissions are classified according to the mechanism of scission process: hydrolytic, mechanochemical, thermal, photochemical, or oxidative scission. Others are classified according to their location in the backbone relative to a specific structural feature: α-scission (a scission of the C-C bond alpha to the carbon atom of a photo-excited carbonyl group), β-scission (a scission of the C-C bond beta to the carbon atom bearing a radical), etc.

A chemical reaction that is induced by direct absorption of mechanical energy on a molecular scale.

Shearing, stretching, and grinding are typical methods of mechanochemical generating of reactive sites, usually macroradicals, in polymer chains.

1. Chemical reactions that are induced by a reactive intermediate (e.g., radical, carbene, nitrene, or ionic species) generated from a photo-excited state are sometimes dealt with as a part of photochemistry.

2. A typical example of the above case in polymer fields is phtopolymerization.

3. See also Definitions 1.1, 3.15, 3.27.

A process that results in the formation of a polymer-polymer complex (see Definition 1.6 in [9]) or a complex composed of a polymer and a low-molar-mass substance.

A chemical reaction in which at least one of the reacting species is a high-molar-mass substance.

A chemical reaction in which at least one reacting species or a catalyst is chemically bound to or dispersed in a polymer.

1. Easy separation of reaction products from reactants or catalyst or both is a great advantage of polymer-supported reactions.

2. Typical examples of polymer-supported reactions are: (a) reactions performed by use of polymer-supported catalysts, (b) solid-phase peptide synthesis, in which intermediate peptide molecules are chemically bonded in pores or on the surface of beads of a suitable polymer support.

Temporary transformation of a reactive group in a reactant (polymer molecules) into a group of negligible reactivity in order to prevent its interference during another reaction.

For example trimethylsilylation is a typical way to protect reactive hydrogen atoms such as in hydroxy or terminal ethynyl groups.

A chemical reaction that is induced by irradiation of a compound or a mixture of compounds with γ-ray, X-ray, electron-beam, or other high-energy beam sources.

1. Typical polymer reactions induced by irradiation are chain scission and crosslinking.

2. Photochemical reaction (see Definition 1.13) is occasionally included in radiation reaction. However, a radiation reaction is usually concerned with the chemical effect of ionizing radiation.

A mixing process that is accompanied by chemical reaction(s) of the components of a polymer mixture.

1. Examples of reactive blending are: (a) blending accompanied by formation of polymer-polymer complex, (b) formation of block or graft copolymers by a combination of radicals formed by mechanochemical scission of respective polymers during blending.

2. Reactive blending may also be carried out as a reactive extrusion or reaction injection molding (RIM).

A process through which a polymer network is formed by a gradual change of liquid monomer(s) into a polymeric sol, to a gel, and in most cases finally to a dry network. (see Definitions 1.9, 2.11 in [10] and 1.58 in [2])

1. An inorganic polymer, e.g., silica-gel or organic/inorganic hybrid, can be prepared by the sol-gel process. (see [10])

2. When the sol-gel process proceeds inside micelles, microgel particles are formed.

3. A sol is a colloidal suspension of a solid in a liquid. The colloidal particles are of such a size that, due to Brownian motion, they are stable in solution without aggregation or precipitation.

4. A gel is a polymer network swollen in a liquid.

A process in which a polymer surface is chemically modified by generation of active sites that can lead to initiation of a graft polymerization or a grafting reaction.

Chemical crosslinking of high-molar-mass linear or slightly branched polymers to give a polymer network with viscoelastic or rubber elastic (entropy elastic) properties.

A classic example of vulcanization is the crosslinking of cis-polyisoprene through sulfide bridges in the thermal treatment of natural rubber with sulfur or a sulfur-containing compound.

A polymer composed of molecules containing ligand groups capable of forming chelates through two or more coordination bonds with a central metal ion (see [7], p. 68).

Chelating polymers mostly act also as ion-exchange polymers specific to ions that form chelates with chelating ligands of the polymer.

A network polymer possessing fixed ionic groups (polyanion or polycation) that are able to exchange counterions (cations or anions) with the ionic components of a solution (see [7], p. 208).

1. Synthetic ion-exchange organic polymers are often called network polyelectrolytes.

2. A membrane possessing ion-exchange groups is called an ion-exchange membrane.

A polymer with stable polymerization-active sites formed in a chain polymerization in which irreversible chain transfer and chain termination are absent (see Definition 3.21 in [2], and Definition 60 in [4]).

A polymer or oligomer that has one reactive group, often at the end, which enables it to act as a monomer; each macromonomer molecule is attached to the main chain of the final polymer by reaction of only one monomeric unit in the macromonomer molecule.

2. See Definition 1.9 in [2] and Definition 61 in [4].

3. Macromonomers are also sometimes referred to as macromers^®. The use of macromer^® is strongly discouraged.

4. The terms "comb polymers" and "graft polymers" are frequently used interchangeably.

A polymer that exhibits catalytic activity.

1. Various synthetic polymer catalysts mimic enzymes.

2. Poly(4-vinylpyridine) and sulfonated polystyrene are examples of polymers that act as catalysts in some base- and acid- catalysed reactions, respectively.

A complex comprising a metal and one or more polymeric ligands.

A polymer that acts as the phase-transfer catalyst, causing a significant enhancement of the rate of a reaction between two reactants located in different immiscible phases owing to the extraction of one of reactants across the interface to the other phase where the reaction takes place.

Polymer phase-transfer catalysts in bead form are often referred to as triphase catalysts because such catalysts form the third phase of the reaction system.

A catalyst system comprising a polymer support in which catalytically active species are dispersed (e.g. metal clusters) or immobilized through chemical bonds or weak interactions such as hydrogen bonds or donor-acceptor interaction.

1. A polymer-supported catalyst is mostly based on a network polymer in bead form, which is easy to separate from liquid media and can be used repeatedly.

2. Examples of polymer-supported catalysts are: (a) a polymer-metal complex that can act as a coordination catalyst, (b) colloidal palladium dispersed in a swollen network polymer that can act as a hydrogenation catalyst. Polymer-supported enzymes are also polymer-supported catalysts.

A reactant (reagent) that has or is attached to a high-molar-mass linear chain or a network.

A polymer or oligomer capable of entering, via reactive groups, into further polymerization; the reactive species thereby contributes more than one monomeric unit to at least one chain of the final polymer.

See Definition 2.37 in [2].

A polymer having chemical groups that can be transformed into other chemical groups under the specific conditions required for a given reaction or application.

A polymer containing groups that can be reversibly reduced or oxidized.

1. Reversible redox reaction can take place in the polymer main chain such as in the case of polyaniline and quinone/hydroquinone polymers, or on side groups such as in the case of a polymer carrying ferrocene side groups.

2. See [7] p. 346.

A term used for soft solid or highly viscous substances, usually containing prepolymers with reactive groups.

1. This term was used historically because of its analogy with natural resins (rosin), and was once used in a broad sense to designate any polymer that is a basic material for plastics, organic coatings, or laquers. However, it became used more recently in a narrow sense to refer to thermosetting polymers and some soft network polymers, especially those in bead form.

2. It is sometimes used not only for prepolymers of thermosets (thermosetting polymers) but also for cured network polymers (thermosets), e.g., epoxy resin, phenolic resin. The ambiguous use of the term in this context for thermosets is strongly discouraged.

3. Another example of use of the term "resin" is to describe the spherical suspension-polymerized beads widely used in the solid-phase synthesis and as polymer supports, catalysts, reagents, and scavengers.

4. See also [8].

A prepolymer capable of entering into further polymerization via its reactive end-groups (see Definition 1.11 in [2]).

The cured product of a thermosetting polymer is called a thermoset.

A polymer susceptible to degradation (see Definition 16 in [5]) that is accompanied by a lowering of its molar mass due to the interaction with enzymes, bacteria, or other biological systems.

A polymer that exhibits electric conductivity similar to that of metals or solutions of electrolytes (see [7], p. 84).

1. The electric conductivity of a conjugated polymer is markedly increased by doping it with an electron donor or acceptor, such as in the case of polyacetylene doped with iodine.

2. A polymer showing a substantial increase in electric conductivity upon irradiation with ultraviolet or visible light is called a photoconductive polymer; an example is poly(N-vinylcarbazole).

3. A polymer that shows electric conductivity due to transport of ionic species is called an ion-conducting polymer; an example is sulfonated polyaniline. When the transporting ionic species is proton as, e.g., in the case of fuel cells, it is called a proton-conducting polymer.

4. A polymer that shows electric semiconductivity is called a semiconducting polymer.

5. Electric conductivity of an insulating polymer can be achieved by dispersing conducting particles (e.g., metal, carbon black) in the polymer. The resulting materials are referred to as conducting polymer composites or polymer-electrolyte composites.

A polymeric material that shows luminescence when an electric current passes through it such that charge carriers can combine at luminescent sites to give rise to an electronically excited state of luminescent groups or molecules.

Electroluminescent polymers are often made by incorporating luminescent groups or dyes into conducting polymers.

A polymer in which spontaneous polarization (see [7], p. 153) arises when individual dipoles become arranged parallel to adjacent dipoles.

Poly(vinylidene fluoride) is an example of a ferroelectric polymer showing strong piezoelectricity after poling.

A polymer that exhibits specified chemical reactivity or has specified physical, biological, pharmacological, or other uses.

Typical functions of functional polymers are catalytic activity, selective binding of particular species, capture and transport of electric charge carriers or energy, convertion of light into charge carriers and vice versa, transport of immobilized drugs to a particular tissue cell in which a drug is released, etc.

A polymeric material whose impact resistance and toughness have been increased by the incorporation of microphase domain of another, softer material.

An example is incorporation of soft polybutadiene domain into glassy polystyrene to give high impact polystyrene.

A polymer that can exhibit one or more fluid state(s) with long-range orientational order over a certain range of temperatures (thermotropic liquid-crystalline polymer) or solution concentrations (lyotropic liquid-crystalline polymer).

See Definition 6.1 in [11].

A solid or soft polymer that includes large number of macropores (50 nm - 1 µm in diameter) where reactions occur effectively or the substrate molecules in a solvent are discriminated according to their size.

1. Typical macroporous polymers are network polymers in bead form. However, linear polymers such as polybenzimidazoles can also be prepared in the form of macroporous polymer beads.

2. Macroporous polymers are used, e.g., as supports for catalysts or reagents and as stationary phases in size-exclusion-chromatography columns.

3. Porous polymers with pore dimeters from ca 2 to 50 nm are called mesoporous polymers.

A polymer that exhibits an optical effect brought about by electromagnetic radiation, the magnitude of which is not proportional to the irradiation intensity (see [7], p. 275).

1. An example of non-linear-optical effects is generation of higher harmonics of the incident light wave on exposure to light.

2. A polymer that exhibits a non-linear optical effect when subjected to electric field is called an electrooptical polymer. Photorefractive polymers exhibit a non-linear optical effect by combination of photoconductivity and electrooptical effect.

A polymer capable of rotating the polarization plane of a transmitted beam of plane-polarized light (see [7], p. 282).

The optical activity originates from the presence of chirality centers in a polymer or from some long-range conformational order in a polymer e.g., helicity (see [7], p. 182).

A polymer that shows reversible stress birefringence.

A polymer that emits fluorescence or phosphorescence after photoexcitation to a higher electronic state.

A polymer that responds to ultraviolet or visible light by exhibiting a change in its molecular shape (photoresponsive polymer), a change in its chemical structure (photoreactive polymer), or a reversible change in color (photochromic polymer), etc.

A polymer that exhibits a change in dielectric properties by application of pressure or shows a change in dimension induced by applied electric field.

A polymer having chemical groups that can dissociate into ions in either solution or melt.

1. A polymer bearing both anionic and cationic groups on its polymer chain is called an amphoteric polyelectrolyte.

2. A polymer having strongly acidic or strongly basic groups on its polymer chain is called a polymer acid or a polymer base, respectively.

3. A solid polymer acid can be used as a matrix for ion-conducting polymers.

A polymer that adsorbs certain substance(s) from a surrounding phase.

A polymeric additive that, when added to a blend of immiscible polymers, modifies their interfaces and stabilizes the blend (see Definition 1.37 in [9]).

Typical polymer compatibilizers are block or graft copolymers.

A polymer that contains either an ionically or covalently bonded molecules of a drug or pharmacologically active groupings and moieties.

A polymer drug is usually used to provide targeted drug delivery to and controlled release of active drug at the target sites of an organism.

A polymer network, including a physical one (see Definition 1.58 in [2]), swollen or capable of being swollen in a liquid.

A thin piece of polymeric material that acts as a barrier permitting selective mass transport.

An example of polymer solvents is poly(oxyethylene), which can solvate various inorganic salts.

A polymer, frequently a polymer network, in which reacting species or catalyst is chemically immobilized, dispersed, or associated.

1. A polymer support is usually prepared by suspension polymerization to give bead form.

2. The location of active sites in a polymer support depends on the type of polymer support. In swollen gel beads the active sites are distributed evenly, whereas in macroporous beads they are predominantly on the internal surface of macropores.

A polymer that lowers the interfacial tension in the system in which it is dissolved by surface enrichment (see [7], p. 409).

A polymeric material that, when irradiated, undergoes a profound change in solubility or is ablated.

1. A resist material can under irradiation either form patterns directly or lead to pattern formation.

2. A resist material that is optimized for use with ultraviolet or visible light, an electron beam, an ion beam, or X-rays is called a photoresist, electron-beam resist, ion-beam resist, or X-ray resist, respectively.

3. In a positive-tone resist, also called a positive resist, the material in irradiated area is removed, which results in an image with a pattern identical with that on the mask. In a negative-tone resist, also called a negative resist, the non-irradiated area is removed, which results in an image that is the reverse of that on the mask.

A polymer which, upon heating above the glass-transition or melting temperature, resumes the shape that it had before the last plastic deformation.

Crystalline trans-polyisoprene is an example of a shape-memory polymer.

A polymer that, relative to its own weight, can absorb and retain extremely large amounts of water, organic solvents, or low-molar-mass compounds.

1. The swelling:weight ratio of a superabsorbent polymer can reach the order of 10³:1.

2. The affinity of a superabsorbent polymer varies with the substance being observed.

3. Superabsorbent polymers are frequently polyelectrolytes (see [12]).