Introduction to Ionomers

by Eisenberg, Adi; Kim, Joon-Seop

• ISBN13: 9780471246787
• ISBN10: 0471246786
• Edition: 1st
• Format: Hardcover
• Copyright: 1998-05-06
• Publisher: Wiley-Interscience

Summary

A practical introduction to one of today's most exciting and rapidly growing areas of polymer science. Introduction to Ionomers affords chemists, engineers, and graduate students an opportunity to familiarize themselves quickly and thoroughly with one of today's most commercially important classes of polymers. Featuring a balanced, fully integrated presentation of basic science and state-of-the-art applications, the book provides the depth of knowledge researchers need to make optimal use of established ionomeric processes or to develop new systems of their own. The book's primary conceptual thrust is the relationship between polymeric architecture and polymeric morphology and properties when affected by ionic groups. While it provides in-depth coverage of all common classes of ionomeric materials--including polystyrenes, polyethylenes, polyurethanes, and polyacrylics--non-crystalline materials are emphasized over partly-crystalline materials. Co-author Adi Eisenberg, a leading ionomer pioneer and innovator, provides a uniquely intimate historical perspective on the field as it has developed over the past three decades. Newcomers to ionomers will appreciate the authors' clear and methodical presentations of difficult concepts, designed to promote rapid mastery of the core principles involved. The product of an exhaustive survey of the huge and rapidly growing world literature on the subject, Introduction to Ionomers is also an excellent resource for experienced professionals attempting to stay abreast of important recent developments in the field.

Author Biography

ADI EISENBERG, PhD, is Otto Maass Professor of Chemistry at McGill University in Montreal, Canada.<br> <br> EOP KIM, PhD, is Assistant Professor in the Department of Polymer Science and Engineering at Chosun University in Kwangju, Korea.

Table of Contents

PREFACE	xiii	(2)
LIST OF SYMBOLS AND ABBREVIATIONS	xv
1 INTRODUCTION	1	(16)
1.1. Definitions	2	(1)
1.2. Nomenclature	3	(1)
1.3. Historical Aspects	4	(3)
1.4. Reasons for Interest in Ionomers	7	(1)
1.5. Aims of the Presentation	8	(1)
1.6. Ionic Interactions	9	(1)
1.7. Sizes of Ionic Groups	9	(2)
1.8. Methods of Expressing Ion Concentrations	11	(1)
1.9. Topics Omitted from This Treatment	12	(1)
1.10. Order of Presentation	12	(1)
1.11. References	13	(4)
2 STRUCTURAL VARIABILITY IN IONOMERS	17	(21)
2.1. Architectural Variation	17	(11)
2.1.1. Monochelics, Telechelics, and Block Copolymers	17	(1)
2.1.1.1. Single Ions at Chain Ends	17	(2)
2.1.1.2. Telechelics	19	(1)
2.1.1.3. Block Copolymers	20	(3)
2.1.2. Simple Random Copolymers	23	(2)
2.1.3. Other Ionomer Families	25	(1)
2.1.3.1. Chains with Regularly Spaced Ions	25	(1)
2.1.3.2. Combs	25	(3)
2.1.3.3. Grafts	28	(1)
2.1.3.4. Polymer-Salt Mixtures	28	(1)
2.2. Chemical Structures	28	(6)
2.2.1. Type of Attachment of Pendent Ion	28	(1)
2.2.2. Nature of Pendent Ions	29	(1)
2.2.3. Counterions	30	(2)
2.2.4. The Nonionic Host Polymer	32	(1)
2.2.5. Inorganic Systems	33	(1)
2.3. Concluding Comments	34	(1)
2.4. References	34	(4)
3 MORPHOLOGY OF RANDOM IONOMERS	38	(21)
3.1. Multiplets	38	(7)
3.1.1. Size and Shape of Multiplet	38	(1)
3.1.1.1. Energetics	38	(1)
3.1.1.2. Solid Angle and Contact Surface Area Concepts	39	(1)
3.1.1.3. Shapes of Multiplets	39	(1)
3.1.1.4. Effect of Ion Content and Dielectric Constant	40	(1)
3.1.1.5. Other Factors	40	(1)
3.1.2. Arrangements of Ion Pairs	40	(1)
3.1.3. Arrangement of the Multiplets	41	(1)
3.1.3.1. Small-Angle Ionic Peak	41	(1)
3.1.3.2. Multiplet-Cluster Concept	42	(1)
3.1.3.3. Hard-Sphere Model	42	(1)
3.1.3.4. Core-Shell Model	42	(1)
3.1.3.5. Dilemma of Hard-Sphere and Core-Shell Models	43	(1)
3.1.3.6. Morphological Continuity and Mechanical Properties	44	(1)
3.2. EHM Model	45	(5)
3.2.1. Restricted Mobility Region	45	(2)
3.2.2. New Cluster Concept	47	(2)
3.2.3. Prevalent Intermultiplet Distance	49	(1)
3.2.4. Semiquantitative Aspects	49	(1)
3.3. Experimental Corroboration	50	(4)
3.3.1. Small-Angle X-Ray Scattering Peak	50	(1)
3.3.2. Dynamic Mechanical Studies	51	(1)
3.3.3. Volume Fraction of Clusters	52	(1)
3.3.4. Thickness of the Restricted Mobility Layer	52	(1)
3.3.5. Unclustered Materials and Homoblends	53	(1)
3.3.6. Experimental Evidence for Reduced Mobility	53	(1)
3.4. Coil Dimensions in Random Ionomers	54	(1)
3.5. References	55	(4)
4 GLASS TRANSITIONS IN RANDOM IONOMERS	59	(27)
4.1. Effect of Ionic Forces	59	(2)
4.2. Glass Transition Versus Electrostatic Work	61	(1)
4.3. Two Glass Transitions	62	(3)
4.3.1. Two Loss Tangent Peaks	63	(1)
4.3.2. Two Glass Transitions by DSC	63	(2)
4.3.3. Expansion Coefficients	65	(1)
4.4. Matrix Glass Transition	65	(10)
4.4.1. The Charge/Distance Effect	65	(4)
4.4.2. Glass Transition Versus Percent Neutralization	69	(1)
4.4.3. Copolymerization, Cross-linking, and Filler Effects	69	(2)
4.4.4. Change in Glass Transition as a Function of Change in Ion Concentration	71	(1)
4.4.5. Ammonium Counterions	72	(1)
4.4.6. Internal Plasticization Effect	73	(1)
4.4.7. Semicrystalline Materials	74	(1)
4.4.8. Theories	74	(1)
4.5. Cluster Glass Transition	75	(8)
4.5.1. Effect of Immobilization	75	(2)
4.5.2. Differences in the Two Glass Transition Temperature Values	77	(2)
4.5.3. Homoblends	79	(2)
4.5.4. Unclustered Materials	81	(1)
4.5.5. Differences in Clustering Behavior of Styrene Ionomers	81	(1)
4.5.6. Mechanism of the Cluster Glass Transition	82	(1)
4.6. References	83	(3)
5 STYRENE IONOMERS	86	(63)
5.1. Stress-Relaxation of Sodium Methacrylate Systems	87	(2)
5.2. Dynamic Mechanical Studies of Sodium Methacrylate Systems	89	(6)
5.2.1. Glassy Modulus	89	(1)
5.2.2. Loss Tangent Peaks	89	(1)
5.2.3. Ionic Modulus	90	(1)
5.2.4. Cross-Linking	90	(2)
5.2.5. Filler	92	(2)
5.2.6. Percolation	94	(1)
5.3. Melt Rheology of Sodium Methacrylate Systems	95	(1)
5.4. Viscoelasticity of Other Carboxylated Ionomers	96	(5)
5.4.1. P(S-co-ANa) versus P(S-co-MANa)	98	(1)
5.4.2. P(S-co-SCNa) versus P(S-co-MANa)	98	(1)
5.4.3. Combs	99	(2)
5.5. Pendent Ion Effect on Viscoelasticity	101	(8)
5.5.1. Sulfonated Ionomers	101	(3)
5.5.2. Benzyloxy or Phenoxy Ionomers	104	(1)
5.5.3. Vinylpyridinium Methyl Iodide Ionomers	105	(1)
5.5.4. Homoblends	106	(3)
5.6. Effects of Various Other Parameters	109	(5)
5.6.1. Dielectric Constant	109	(1)
5.6.2. Counterions	110	(1)
5.6.3. Molecular Weight	111	(1)
5.6.4. Degree of Neutralization	111	(3)
5.7. Ion Hopping	114	(3)
5.8. Other Physical Properties and Spectroscopy	117	(19)
5.8.1. Density	117	(1)
5.8.2. Dielectric Properties	118	(4)
5.8.3. Spectroscopy	122	(1)
5.8.3.1. Infrared	122	(3)
5.8.3.2. Raman	125	(1)
5.8.3.3. Nuclear Magnetic Resonance	125	(1)
5.8.3.4. Electron Spin Resonance	126	(1)
5.8.3.5. Extended X-Ray Absorption Fine Structure	127	(2)
5.8.4. Orientation	129	(2)
5.8.5. Gas Transport	131	(1)
5.8.6. Water Absorption	132	(1)
5.8.7. Transport of Nongaseous Materials	133	(3)
5.9. Fatigue and Fracture Properties	136	(1)
5.10. Nonequilibrium Behavior	137	(4)
5.11. Chemistry in Ionomers	141	(2)
5.11.1. Stability	141	(2)
5.11.2. Reactions in Ionomers	143	(1)
5.12. References	143	(6)
6 PARTLY CRYSTALLINE IONOMERS	149	(41)
6.1. Polyethylene	150	(14)
6.1.1. Stress-Relaxation	150	(1)
6.1.2. Dynamic Mechanical Properties	151	(1)
6.1.3. Melt Rheology	152	(1)
6.1.4. Other Mechanical Properties	153	(1)
6.1.5. Dielectric Properties	153	(3)
6.1.6. Spectroscopy	156	(1)
6.1.6.1. Infrared	156	(2)
6.1.6.2. Raman	158	(1)
6.1.6.3. Electron Spin Resonance	158	(1)
6.1.6.4. Nuclear Magnetic Resonance	159	(1)
6.1.7. Water Uptake	160	(1)
6.1.8. Crystallinity	160	(2)
6.1.9. Permeation	162	(1)
6.1.10. Orientation	163	(1)
6.1.11. Concluding Comments	164	(1)
6.2. Polytetrafluoroethylene	164	(19)
6.2.1. Crystallinity	165	(1)
6.2.2. Mechanical Properties	166	(3)
6.2.3. Other Physical Properties	169	(2)
6.2.4. Dielectric Properties	171	(1)
6.2.5. Spectroscopy	172	(1)
6.2.5.1. Nuclear Magnetic Resonance	172	(1)
6.2.5.2. Infrared	172	(1)
6.2.6. Morphology	173	(2)
6.2.7. Water Uptake and Diffusion	175	(4)
6.2.9. Permeation	179	(3)
6.2.10. Chemistry	182	(1)
6.3. Polypentenamer	183	(1)
6.3.1. Synthesis and Thermal Properties	183	(1)
6.3.2. Mechanical Properties	183	(1)
6.3.3. Morphology	184	(1)
6.4. References	184	(6)
7 OTHER IONOMERS	190	(54)
7.1. Ionomers with Statistical Ion Placement	190	(24)
7.1.1. Elastomers	190	(1)
7.1.1.1. Butadiene-Based Elastomers	190	(2)
7.1.1.2. Ethylene-Propylene-Diene Terpolymers	192	(1)
7.1.1.3. Polyurethane Ionomers	193	(1)
7.1.3.1.1. Physical Properties	194	(8)
7.1.1.3.2. Morphology	202	(2)
7.1.2. Acrylate and Methacrylate Ionomers	204	(5)
7.1.3. Zwitterionic Systems	209	(1)
7.1.3.1. Siloxane-Based Di-Zwitterionomers	209	(1)
7.1.3.2. Hydrocarbon-Based Zwitterionomers	210	(4)
7.2. Ionomers with Regular Architectures	214	(24)
7.2.1. Block Ionomers	214	(1)
7.2.1.1. Morphology	214	(4)
7.2.1.2. Mechanical Properties	218	(2)
7.2.2. Monochelics, Telechelics, and Stars	220	(1)
7.2.2.1. Monochelics	221	(1)
7.2.2.2. Telechelics	221	(3)
7.2.2.3. Stars	224	(5)
7.2.3. Ionenes	229	(4)
7.2.4. Polymer-Salt Mixtures	233	(5)
7.3. References	238	(6)
8 PLASTICIZATION	244	(23)
8.1. Small Molecule Plasticizers of High Polarity	245	(5)
8.1.1. Mechanical Properties	245	(3)
8.1.2. Morphology	248	(2)
8.2. Plasticizers of Low Polarity	250	(6)
8.2.1. Small Molecule Plasticizers	250	(1)
8.2.1.1. Mechanical Properties	250	(4)
8.2.1.2. Morphology	254	(1)
8.2.2. Oligomeric Plasticizers	255	(1)
8.3. Amphiphilic Plasticizers	256	(6)
8.3.1. Surfactants	256	(2)
8.3.2. Oligomeric Amphiphiles	258	(1)
8.3.2.1. Mechanical Properties	258	(2)
8.3.2.2. Morphology	260	(1)
8.3.3. Amines	261	(1)
8.4. Internal Plasticization	262	(2)
8.4.1. Mechanical Properties	262	(1)
8.4.2. Morphology	263	(1)
8.5. Summary	264	(1)
8.6. References	265	(2)
9 IONOMER BLENDS	267	(40)
9.1. Techniques for Characterizing Miscibility	268	(1)
9.2. Menu of Interactions	269	(3)
9.3. Morphology	272	(1)
9.4. Cross-linking and Plasticization	272	(2)
9.5. Ion-Ion Blends	274	(6)
9.6. Ion Pair-Ion Pair Blends	280	(2)
9.7. Ion-Dipole Blends	282	(7)
9.8. Ion-Coordination Blends	289	(7)
9.9. Miscellaneous Blends	296	(6)
9.9.1. Telechelic Blends	296	(3)
9.9.2. Blends of Ionomers with Their Nonionic Parent Polymers	299	(2)
9.9.3. Styrene Ionomer-Poly(Phenylene Oxide) Blends	301	(1)
9.10. Concluding Remarks	302	(1)
9.11. References	302	(5)
10 APPLICATIONS	307	(8)
10.1. Membranes and Thin Films	307	(4)
10.1.1. Membranes	307	(1)
10.1.2. Packaging	308	(1)
10.1.3. Fertilizer	309	(1)
10.1.4. Floor Polish	309	(1)
10.1.5. Imaging Systems	310	(1)
10.1.6. Magnetic Recording Media	311	(1)
10.1.7. Adhesives	311	(1)
10.2. Ionomers in Bulk	311	(1)
10.2.1. Plastics	311	(1)
10.2.2. Elastomers	312	(1)
10.3. Drilling Fluids	312	(1)
10.4. Catalysts and Catalytic Supports	312	(1)
10.5. References	313	(2)
INDEX	315