Fundamental Principles of Polymeric Materials, 2nd Edition

by Stephen L. Rosen (Univ. of Missouri-Rolla)

• ISBN13: 9780471575252
• ISBN10: 0471575259
• Edition: 2nd
• Format: Hardcover
• Copyright: 1993-01-01
• Publisher: Wiley-Interscience

Summary

Revised due to new developments in the polymer area. This book contains a broad, unified introduction to the subject matter that will be of immediate practical value plus a foundation for more advanced study. New features include a discussion of liquid-crystal polymers, the Flory-Huggins theory, group-transfer polymerization, a quantitative treatment of Ziegler-Natta polymerization with three new worked-out examples and much more. Also, end-of-chapter problems have been added along with practical illustrations of the material.

Table of Contents

Introduction	1	(6)
References	4	(1)
Problems	4	(3)
PART 1 POLYMER FUNDAMENTALS	7	(112)
Types of Polymers	9	(19)
Reaction to Temperature	9	(1)
Chemistry of Synthesis	10	(5)
Structure	15	(13)
Reference	25	(1)
Problems	25	(3)
Bonding in Polymers	28	(4)
Types of Bonds	28	(1)
Bond Distances and Strengths	28	(1)
Bonding and Response to Temperature	29	(2)
Action of Solvents	31	(1)
References	31	(1)
Stereoisomerism	32	(7)
Introduction	32	(1)
Stereoisomerism in Vinyl Polymers	32	(5)
Stereoisomerism in Diene Polymers	37	(2)
Reference	38	(1)
Problems	38	(1)
Polymer Morphology	39	(14)
Requirements for Crystallinity	39	(1)
The Fringed Micelle Model	40	(2)
Lamellar Crystals	42	(1)
The Effect of Crystallinity on Mechanical Properties	43	(3)
The Effect of Crystallinity on Optical Properties	46	(1)
Extended-Chain Crystals	47	(1)
Liquid-Crystal Polymers	48	(2)
Spherulites	50	(3)
References	51	(1)
Problems	51	(2)
Characterization of Molecular Weight	53	(29)
Introduction	53	(1)
Average Molecular Weights	53	(5)
Determination of Average Molecular Weights	58	(10)
Molecular Weight Distributions	68	(4)
Size-Exclusion Chromatography	72	(10)
References	77	(1)
Problems	78	(4)
Polymer Solubility and Solutions	82	(21)
Introduction	82	(1)
Typical Phase Behavior in Polymer-Solvent Systems	82	(1)
General Rules for Polymer Solubility	83	(2)
The Thermodynamic Basis of Polymer Solubility	85	(1)
The Solubility Parameter	86	(2)
Hansen's Three-Dimensional Solubility Parameter	88	(3)
The Flory-Huggins Theory	91	(2)
A Promising Recent Approach	93	(1)
Properties of Dilute Solutions	94	(2)
Polymer-Polymer-Common Solvent Systems	96	(1)
Concentrated Solutions: Plasticizers	97	(6)
References	100	(1)
Problems	101	(2)
Transitions in Polymers	103	(16)
The Glass Transition	103	(1)
Molecular Motions in an Amorphous Polymer	103	(1)
Determination of Tg	104	(2)
Factors That Influence Tg	106	(3)
The Effect of Copolymerization on Tg	109	(1)
The Thermodynamics of Melting	109	(3)
The Metastable Amorphous State	112	(1)
The influence of Copolymerization on Properties	113	(1)
General Observations About Tg and Tm	114	(1)
Effects of Cross-linking	114	(1)
Other Transitions	115	(4)
References	115	(1)
Problems	115	(4)
PART 2 POLYMER SYNTHESIS	119	(112)
Step-Growth (Condensation) Polymerization	121	(14)
Introduction	121	(1)
Statistics of Linear Step-Growth Polymerization	122	(1)
Number-Average Chain Lengths	123	(2)
Chain Lengths on a Weight Basis	125	(2)
Gel Formation	127	(4)
Kinetics of Polycondensation	131	(4)
References	132	(1)
Problems	133	(2)
Free-Radical Addition (Chain-Growth) Polymerization	135	(41)
Introduction	135	(1)
Mechanism of Polymerization	135	(2)
Kinetics of, Homogeneous Polymerization	137	(6)
Instantaneous Average Chain Lengths	143	(1)
Temperature Dependence of Rate and Chain Length	144	(1)
Chain Transfer	145	(4)
Instantaneous Distributions in Free-Radical Addition Polymerization	149	(6)
Instantaneous Quantities	155	(1)
Cumulative Quantities	156	(3)
Relations Between Instantaneous and Cumulative Average Chain Lengths for a Batch Reactor	159	(4)
Emulsion Polymerization	163	(3)
Kinetics of Emulsion Polymerization in Stage II, Case 2	166	(10)
References	171	(1)
Problems	172	(4)
Nonradical Addition Polymerization	176	(24)
Cationic Polymerization	176	(1)
Anionic Polymerization	177	(6)
Anionic Kinetics	183	(3)
Group-Transfer Polymerization	186	(1)
Heterogeneous Stereospecific Polymerization	187	(13)
References	196	(1)
Problems	196	(4)
Copolymerization	200	(14)
Mechanism	200	(2)
Significance of Reactivity Ratios	202	(1)
Variation of Composition with Conversion	203	(6)
Copolymerization Kinetics	209	(1)
Penultimate Effects and Charge-Transfer Complexes	210	(4)
References	210	(1)
Problems	211	(3)
Polymerization Practice	214	(17)
Bulk Polymerization	214	(5)
Gas-Phase Olefin Polymerization	219	(2)
Solution Polymerization	221	(2)
Interfacial Polycondensation	223	(1)
Suspension Polymerization	223	(3)
Emulsion Polymerization	226	(5)
References	228	(1)
Problems	228	(3)
PART 3 POLYMER PROPERTIES	231	(120)
Rubber Elasticity	233	(11)
Introduction	233	(1)
Thermodynamics of Elasticity	233	(7)
Statistics of Ideal Rubber Elasticity	240	(4)
References	242	(1)
Problems	242	(2)
Purely Viscous Flow	244	(21)
Introduction	244	(1)
Basic Definitions	244	(3)
Relations Between τ and γ: Flow Curves	247	(1)
Time-Dependent Behavior	248	(1)
Polymer Melts and Solutions	249	(1)
Quantitative Representation of Flow Behavior	250	(5)
Temperature Dependence of Flow Properties	255	(3)
Influence of Molecular Weight on Flow Properties	258	(1)
The Effects of Pressure on Viscosity	259	(6)
References	260	(1)
Problems	261	(4)
Viscometry and Tube Flow	265	(24)
Introduction	265	(1)
Viscous Energy Dissipation	265	(1)
Poiseuille Flow	266	(4)
Determination of Flow Curves	270	(2)
Entrance Corrections	272	(3)
Scaleup for Laminar Flow in Cylindrical Tubes	275	(1)
The Couette Viscometer	276	(1)
Cone-and-Plate Viscometer	277	(2)
Disk-Plate Viscometer	279	(2)
Turbulent Flow	281	(1)
Drag Reduction	282	(7)
References	284	(1)
Problems	285	(4)
Introduction to Continuum Mechanics	289	(9)
Three-Dimensional Stress and Strain	289	(1)
General Constitutive Relations	290	(1)
Equilibrium Viscometric Flows	291	(3)
Interpretation of the Normal Stresses	294	(4)
References	295	(1)
Problems	296	(2)
Linear Viscoelasticity	298	(53)
Introduction	298	(1)
Mechanical Models for Linear Viscoelastic Response	298	(9)
The Four-Parameter Model and Molecular Response	307	(4)
Viscous or Elastic Response? The Deborah Number	311	(1)
Quantitative Approaches	312	(4)
The Boltzmann Superposition Principle	316	(5)
Dynamic Mechanical Testing	321	(16)
Time-Temperature Superposition	337	(14)
References	343	(1)
Problems	343	(8)
PART 4 POLYMER TECHNOLOGY	351	(58)
Processing	353	(22)
Introduction	353	(1)
Molding	353	(6)
Extrusion	359	(3)
Blow Molding	362	(2)
Rotational, Fluidized-Bed and Slush Molding	364	(1)
Calendering	365	(1)
Sheet Forming (Thermoforming)	366	(1)
Stamping	367	(1)
Solution Casting	367	(1)
Casting	367	(1)
Reinforced Thermoset Molding	368	(1)
Fiber Spinning	369	(2)
Compounding	371	(4)
References	373	(2)
Plastics	375	(14)
Introduction	375	(1)
Mechanical Properties of Plastics	375	(1)
Contents of Plastic Compounds	376	(10)
Sheet Molding Compound	386	(3)
References	387	(2)
Rubber	389	(5)
Introduction	389	(1)
Thermoplastic Elastomers	389	(1)
Contents of Rubber Compounds	390	(1)
Rubber Compounding	390	(4)
References	393	(1)
Synthetic Fibers	394	(3)
Introduction	394	(1)
Fiber Processing	394	(1)
Dyeing	395	(1)
Additives and Treatments	395	(1)
Effects of Heat and Moisture	395	(2)
Surface Finishes	397	(6)
Introduction	397	(1)
Traditional Types of Surface Finishes	397	(2)
Solventless Coatings	399	(2)
Electrodeposition	401	(2)
References	402	(1)
Adhesives	403	(6)
References	406	(3)
Index	409