IUPAC Provisional Recommendations

Transcription

1 1 INTERNATIONAL UNION OF PURE AND APPLIED CHEMISTRY MACROMOLECULAR DIVISION COMMISSION ON MACROMOLECULAR NOMENCLATURE* AND SUB - C O M M I T T E E O N M A C R O M O L E C U L A R T E R M I N O L O G Y * * TERMINOLOGY OF POLYMERS CONTAINING IONIZABLE OR IONIC GROUPS AND OF POLYMERS CONTAINING IONS (IUPAC Recommendations 2004) Prepared by a Working Group consisting of M. Hess (Germany), R. G. Jones (UK), J. Kahovec (Czech Republic), T. Kitayama (Japan), P. K r a t o c h vρ l (Czech Republic), P. Kubisa (Poland), W. Mormann (Germany), R. F. T. Stept o (UK), D. Tabak (Brazil), J. VohlΡ dal (Czech Republic) and E. S. Wilks (USA). P r e p a r e d f o r p u b l i c a t i o n b y P. Kubisa pkubisa@bilbo.cbmm.lodz.pl *Membership of the Commission on Macromolecular Nomenclature (extant until 2002) during the preparation of this report ( ) was as follows: Titular members: M. Barón (Argentina, Titular Member from 1996, Secretary from 1998); K. Hatada (Japan, to 1997, Associate Member to 1999); M. Hess (Germany, Associate Member from 1996, Titular Member from 1998, Chairman from 2000); K. Horie (Japan, Associate Member from 1996, Titular Member from 1998); R. G. Jones (UK, P o o l T i t u l a r M e m b e r t o , T i t u l a r M e m b e r f r o m ) ; J. K a h o v e c ( C z e c h R e p u b l i c, t o ) ; P. K u b i s a ( P o l a n d, Associate Member from 1996, Titular Me mber from 2000); E. Maréchal (France, Titular Member to 1999, Associate M e m b e r ); I. Meisel (Germany, Associate Member from 1998, Titular Member from 2000); W. V. Metanomski (USA, to 1999); C. Noël (France, to 1997); V. P. Shibaev (Russia, Associate Member to 1999); R. F. T. S t e p t o ( U K, Chairman to 1999); E. S. Wilks (USA, Associate Member from 1998, Titular Member from 2000); W. J. Work (USA, Secretary t o ) Associate Members contributing to this report: J. - I l. J i n ( K o r e a, f r o m ) ; T. K i t a yama (Japan, from 2000); S. Penczek (Poland, from 1994); J. VohlΡ dal (Czech Republik, from 2000). National Representative contributing to this report: W. Mormann (Germany, from 2000). Page 1 of 12 DRAFT 23 December 2004

2 2 * * M e m b e r s h i p o f t h e S u b-committee on Macromolecular terminology (exta n t f r o m ) d u r i n g t h e p r e p a r a t i o n o f this report ( ) was as follows: M. Hess (Germany, Chairman ); M. Barón (Argentina, Secretary u n t i l ) ; R. G. J o n e s ( U K, Secretary f r o m ) ; G. Allegra (Italy); A. Fradet (France); J. He (China); K. Horie (Japan); A. D. Jenkins (UK); J.-I. Jin (Korea); R. G. Jones (UK); J. Kahovec (Czech Republic); T. Kitayama (Japan); P. KratochvΡ l (Czech Republic); P. Kubisa (Poland); I. Meisel (Germany); W. V. Metanomski (USA); G. Moad (Australia); W. Mormann (Germany) ; S. P e n c z e k ( P o l a n d ) ; L. P. Rebelo (Portugal); M. Rinaudo (France); I. Schopov (Bulgaria); M. Schubert (USA); V. P. Shibaev (Russia); S. Slomkowski (Poland); R. F. T. Stepto (UK); D. Tabak (Brazil); J. VohlΡ dal (Czech Republik); E. S. Wilks (USA); W. J. Work (USA). Others contributing to this report: B. G r a d y ( U S A ) Republication or reproduction of this report or its storage and/or dissemination by electronic means is permitted without the need for formal IUPAC permission on condition that an acknowledgment, with full reference to the source along with use of the copyright symbol, the name IUPAC and the year of publication are prominently visible. Publication of a translation into another language is subject to the additional condition of prior approval from the relevant IUPAC National Adhering Organization. _ DRAFT 23 December 2004 Page 2 of 12

3 3 INDEX Introduction 4 Terminology of polymers containing ionizable 5 or ionic groups and polymers containing ions R e f e r e n c e s 11 Alphabetical Index of Terms 12 Page Page 3 of 12 DRAFT 23 December 2004

4 INTRODUCTION 4 TERMINOLOGY OF POLYMERS CONTAINING IONIZABLE OR IONIC GROUPS AND OF POLYMERS CONTAINING IONS The document defines the most commonly used terms relating to polymers containing ionizable or ionic groups and to polymers containing ions. Inorganic materials such as phosphates, silicates, etc., that also may be considered ionic polymers are excluded from the present document. Only those terms that could be defined without ambiguity are considered. Terms subsidiary to the main terms, are printed in bold type in notes to the main terms. DRAFT 23 December 2004 Page 4 of 12

5 5 1. ionic polymer ion-containing polymer Polymer composed of macromolecules containing ionic groups irrespective of their nature, content, and location. Note: Polymers composed of macromolecules containing groups that are not ionic but may undergo self - ionization under suitable conditions are customarily included in this class. 2. ionomer Polymer composed of macromolecules in which a small but significant proportion of the c o n s titutional units has ionic or ionizable groups or both. 1. See Definition 1.66 in [2]. 2. Ionic groups are present in sufficient amounts to cause the micro -phase separation of ionic domains from the continuous polymer phase. The ionic domains can act as physical crosslinks. Typically, sufficient means less than 10 % of constitutional units containing ionic or ionizable groups. 3. ionene Polymer composed of macromolecules in which ionized groups are parts of main chains. Note: Most commonly, the ionized groups in ionenes are quaternary ammonium groups. 4. ionic aggregates in an ionomer Domains enriched with ionic groups within an ionomer matrix. 5. critical ion-concentration in an ionomer Concentration of ionic groups in an ionomer matrix, above which ionic aggregation occurs. 6. ionomer multiplet Page 5 of 12 DRAFT 23 December 2004

6 6 Ionic aggregate, in a polymer matrix of low polarity, formed through the association of ion- pairs. 7. ionomer cluster Ionic aggregate, in a polymer matrix of low polarity, formed through interactions of ionomer multiplets. 1. The mobility of the polymer segments surrounding the multiplets is reduced relative to that of bulk material. With increasing ion content the number density of the multiplets increases leading to overlapping of the restricted mobility regions around the multiplets; those regions are referred to as clusters. 2. Typically an ionomer exhibits two glass transition temperatures (T g ), one for nonpolar matrix and the other for clusters. 8. polyelectrolyte Polymer composed of macromolecules in which a substantial portion of the constitutional units contain ionic or ionizable groups, or both. 1. See Definition 1.65 in [2] 2. A different definition, based on the properties of polyelectrolyte, is given i n [ 1 ]. 3. The terms polymeric electrolyte and polymer electrolyte are sometimes used for polyelectrolyte. They should not be confused with the term solid polymer electrolyte (see Definition 20). 4. Polyelectrolytes can be either synthetic or natural. Nucleic acids, proteins, teichoic acids, some polypeptides, and some polysaccharides are examples of natural polyelectrolytes. 9. polyelectrolyte network Polymer network containing ionic or ionizable groups in a significant fraction of its constitutional u n i t s. 1. A polyelectrolyte network is sometimes called a crosslinked polyelectrolyte. Use of the latter term is not recommended unless the polyelectrolyte network is formed by the crosslinking of existing polyelectrolyte macromolecules rather than by nonlinear polymerization (see Definition 1.59 in [2]). 2. In contrast to a polyelectrolyte (see Definition 8), a polyelectrolyte network is insoluble. 3. A polyelectrolyte network in contact with a solution of a salt is able to exchange counterions (c ations or anions) with ionic components of the solution and act as an ion exchanger. Therefore, the term ion-exchange polymer (see Definition 10) is frequently used. DRAFT 23 December 2004 Page 6 of 12

7 7 10. ion-exchange polymer Polymer that has ionic groups, anionic or cationic, and is able to exchange counterions, cations or anions, with the ionic components of a solution. 1. See definition 2.2 in [3] 2. Most commonly, ion-exchange polymers are polyelectrolyte networks (see Definition 9). They are often called ion-exchange resins ; use of the term resin is discouraged (see Definition 2.13 in [3]). 3. Depending on the structure of their acid groups, cation-exchange polymers may be classified as strongly acidic (e.g., containing sulfonic acid groups) or weakly acidic (e.g., c o n t aining carboxylic acid groups). 4. Depending on the structure of their basic groups, anion-exchange polymers may be classified as strongly basic (e.g., containing quaternary ammonium base groups) or weakly basic (e.g., containing amino groups). 11. polyampholyte amphoteric polymer ampholytic polymer Polyelectrolyte (see Definition 8) composed of macromolecules containing both cationic and anionic groups, or corresponding ionizable groups in the same macromolecule. 1. See Definition 3.16 in [3]. 2. A polyampholyte in which ionic groups of opposite sign are incorporated into one pendant group (betaine type structure) is called a polymeric inner salt, zwitterionic polymer o r polybetaine. 12. polyelectrolyte complex P o l y m e r-polymer c omplex composed of macromolecules carrying charges of opposite sign causing the macromolecules to be bound together by electrostatic interactions. Note: Polyelectrolyte complex is also called polysalt. Use of this term is not recommended. Page 7 of 12 DRAFT 23 December 2004

8 8 13. polyacid Polyelectrolyte composed of macromolecules containing acidic groups on a significant fraction of the constitutional units. 1. See Definition 3.16 in [3]. 2. Most commonly, the acidic groups are COOH, -SO 3 H or PO 3 H polybase P o l yelectrolyte composed of macromolecules containing basic groups on a significant fraction of the constitutional units. 1. See Defition 3.16 in [3]. 2. Most commonly, the basic groups are amino groups. 15. cationic polymer polycation Polyme r composed of positively charged macromolecules. 1. If a substantial fraction of constitutional units carries positive charges then a polycation is a polyelectrolyte. 2. The positive charges may be fixed on groups located in main chains as in an i onene (cf. Definition 3) or in pendant groups. 3. Each macromolecule of a cationic polymer is accompanied by its equivalent amount of counteranions. 4. The term cationic polymer should not be used to denote a polymer prepared by cationic polymerization. 16. anionic polymer polyanion Polymer composed of negatively charged macromolecules. 1. If a substantial fraction of constitutional units carries negative charges then a polyanion is a polyelectrolyte. 2. Each macromolecule of an anionic polymer is accompanied by its equivalent amount of countercations. DRAFT 23 December 2004 Page 8 of 12

9 9 3. The term anionic polymer should not be used to denote a polymer prepared by anionic polymerization. 17. halato-telechelic polymer Polymer composed of linear macromolecules having ionic or ionizable end-groups. 1. This term is used to denote a polymer composed of macromolecules having stable (long-lived) ionic or ionizable groups, such as carboxylate or quaternary ammonium groups, as chain ends. It should not be used to describe a polymer composed of macromolecules having chain ends that are transient intermediates in ionic polymerizations initiated by a difunctional initiators. 2. The term halatopolymer i s u s e d for linear polymers formed by the coupling of a halato - telechelic p olymer having, e.g., carboxylate groups with divalent metal cations [4]. 18. electrically conducting polymer Polymeric material that exhibits bulk electric conductivity. 1. See Definition 3.2 in [3] 2. An important class of electrically conduct ing polymers are intrinsically conducting polymers. Such polymers are composed of macromolecules having fully conjugated sequences of double bonds along the chains. Upon acquiring positive or negative charges by oxidation or reduction with suitable electron acceptors or electron donors (charge -transfer agents), they show bulk electrical conductivity comparable to that of some metals. 3. Examples of conjugated, electrically conducting polymers are: polyacetylene, polythiophene, polypyrrole, poly(1,4-phenylene), poly(1,4-phenylene sulfide), poly(1,4 -phenylenevinylene). 4. The oxidation or reduction processes referred to in Note 2 are termed doping. The charge - transfer agents used are termed dopants. Examples of dopants include AsF 5 or I 2 as oxidizing agents, generating cation -radicals on the chains (so-called holes), or a solution of sodium naphthalenide in tetrahydrofuran as a reducing agent, generating anion -radicals on the chains. 5. Unlike polymeric electrolytes in which charges are transported by dissolved ions, the charges in conjugated conducting polymers are transported along and between polymer molecules via generated charge carriers (e.g., holes, electrons). 6. An intrinsically conducting polymer, should be distinguished from a conducting polymer composite (see Definition 19) and from a solid polymer electrolyte (see Definition 20). 19. conducting polymer composite1 Electrically conducting composite comprising a polymer and an electrically conducting material. Note: Most commonly the conducting m aterial is a low-m o l e c u l a r-weight filler (e.g., c a r b o n b l a c k o r metal particles). Page 9 of 12 DRAFT 23 December 2004

10 solid polymer electrolyte Electrically conducting solution of a salt in a polymer. 1. An example of solid polymer electrolyte is a solution of a lithium sa lt in a poly(oxyethylene) matrix; the ionic conductivity of such material is due to the mobility of lithium cations and their counterions in an electric field. 2. Although the adjective "solid" is used, the material may be a liquid. 3. The term solid polymer electrolyte should not be confused with the term polymeric electrolyte (see Definition 8, Note 2). DRAFT 23 December 2004 Page 10 of 12

11 11 References: [1] IUPAC Compendium of Chemical Terminology, The Gold Book, Second Edition. A. D. McNaught and A. Wilkinson, Blackwell Science [ISBN ]. [ 2 ] Glossary of basic terms in polymer science (IUPAC Recommendations 1996) Pure Appl. Chem., 68, (1996). [3] Definition of terms relating to reactions of polymers and to functional polymeric materials (IUPAC Recommendations 2004) Pure Appl. Chem., 76, (2004). [4] Polymer Science Dictionary, M. S. Alger Ed., Elsevier Applied Science, London, New York, Page 11 of 12 DRAFT 23 December 2004

12 12 Alphabetical Index of Terms : ampholytic polymer (11) amphoteric polymer (11) anionic polymer (16) cationic polymer (15) conducting polymer composite (19) critical ion-concentration in an ionomer (5) doping (18) dopant (18) electrically conducting polymer (18) halatopolymer (17) halato-telechelic polymer (17) i n t r i n s i c a lly conducting polymer (18) i o n -containing polymer (1) ionene (3) i o n -exchange polymer (10) ionic aggregates in an ionomer (4) ionic polymer (1) i o n o m e r ( 2 ) i o n o m e r c l u s t e r ( 7 ) ionomer multiplet (6) polyacid (13) polyampholyte (11) polyanion (16) polybase (14) polybetaine (11) polycation (15) polyelectrolyte (8) polyelectrolyte complex (12) polyelectrolyte network (9) polymer electrolyte (8) polymeric electrolyte (8) polymeric inner salt (11) solid polymer electrolyte (20) zwitterionic polymer (11) DRAFT 23 December 2004 Page 12 of 12