Chapter
2.2 Molecular weight distribution
2.2.1 Molecular weight distribution function
2.2.2 Molecular weight distribution in step polymerization
2.2.3 Weight-average molecular weight
2.2.4 Weight-average molecular weight in step polymerization
2.2.5 MW/MN as a measure of dispersity
2.2.6 The exponential approximation to the 'most probable' distribution
2.2.7 The 'Schulz-Zimm' distribution
2.2.8 The distribution of molecular weight in 'living' polymers
2.3 Network formation by non-linear polymers: branching and crosslinking; gelation
2.3.1 The gel point in branched polymers from multifunctional monomers
2.3.2 Crosslinking - random
2.3.3 Crosslinking - end-group
2.3.4 Graph theory and branching
3 Molecular weight determination
3.2 Colligative methods for MN
3.2.1 Boiling point elevation (ebulliometry)
3.2.2 Freezing point depression (cryoscopy)
3.3.3 Solution viscosity and polymer structure
3.4 Light scattering for Mw
3.4.1 The origin of scattering
3.4.2 Molecular weight and scattering
3.5 Molecular weight distribution from chromatography
Appendix A3.1 Scattering of light
A3.1.2 Light scattering from polymer molecules
4 Polymerization: kinetics and mechanism
4.1.1 Self-catalyzed polymerization
4.1.2 Added catalyst polymerization
4.2 Free radical chain polymerization
4.2.1 Kinetic representation
4.2.2 Rate of polymerization
4.2.3 Instantaneous molecular weight
4.2.4 Molecular weight distribution
4.2.5 Thermochemistry and the effect of temperature on radical polymerization
4.2.7 Polymerization to high conversion
4.2.8 Emulsion and suspension polymerization
4.3 Chain copolymerization
4.3.1 Composition of copolymers
4.3.3 Reactivity ratios and chemical structure
4.4 Ionic polymerizations
4.4.1 Anionic polymerization
4.4.2 Cationic polymerization
4.5 Coordination polymerization
4.5.1 Ziegler-Natta catalysis
4.5.2 Supported metal oxides
4.5.3 Coordination copolymerization
4.5.4 Homogeneous Ziegler-Natta systems
5 Three dimensional architecture: conformation and stereochemical configuration
5.1 Conformation: the role of bond rotation in determining molecular shape
5.1.1 Conformational isomerism
5.1.2 Helices and crystals
5.1.3 Melts and solutions
5.2 Stereochemical configuration: the role of stereochemistry in determining molecular shape
5.2.2 Tacticity and conformations
5.2.3 Tacticity and crystallinity
5.2.4 Conformations in melts and solutions
6 The statistical behavior of conformationally disordered chains
6.1.1 The persistence length
6.1.2 The characteristic ratio of the freely rotating chain
6.1.3 The characteristic ratio of the independent bond chain
6.1.4 The effect of interactions between neighboring bonds
6.2 Long phantom chains, the Gaussian coil
6.2.1 The end-to-end vector distribution function
6.2.2 The radius of gyration of the Gaussian chain
6.2.3 The approach of phantom chains to Gaussian statistics with increasing chain length
6.3 The freely jointed chain: the distribution function for an exactly treatable model
6.3.1 The end-to-end vector distribution function
6.3.2 The distribution function for the freely jointed chain
6.3.3 The inverse Langevin function approximation for the freely jointed chain
6.3.4 Comparison among distribution functions for the freely jointed chain
6.3.5 The equivalent freely jointed chain
Appendix A6.1 The Eyring transformation matrix
Appendix A6.2 The inverse Langevin function approximation for the freely jointed chain
Appendix A6.3 Mean-field derivation of the excluded volume expansion of R
7 The interacting bond model for the average properties of coiling chains
7.1 The partition function and scalar averages for a one dimensional chain with interacting bonds
7.2 Averaging of a matrix and matrix products
7.3 The characteristic ratio of long uniform chains
7.4 The characteristic ratio of finite chains
7.5 Illustrative calculations, the three-state chain
7.5.1 Statistical weight matrices
7.5.2 Bond conformational populations
7.5.3 The characteristic ratio of the three-state chain
7.6 Some examples of calculations on actual chains
7.6.1 The characteristic ratio of polyethylene
7.6.2 Conformational statistics for vinyl chains
7.6.3 Characteristic ratios of polypropylenes
7.6.4 Results for some other polymers
8.2 Classical molecular theory of rubber elasticity
8.2.2 The phantom network model
8.2.3 Comparison between the two versions
8.2.4 Stress-strain relations
8.3 Experimental behavior
8.3.1 Stress-strain curves
8.3.2 Stiffness and crosslink density
8.4 Further development of molecular theory
8.4.1 Constrained junction-fluctuation models
8.4.2 Entanglement theories
8.5 The chemistry of crosslinking
8.5.1 Single bond crosslinks - peroxides
8.5.3 More complex crosslinks of similar chemical character to the polymer
8.5.4 More complex crosslinks of different chemical character
8.5.5 Particulate crosslinks
8.6 Structures of elastomers
8.6.1 Glass formation and rubbery behavior
8.6.2 Crystallization and elastomers
8.6.3 Some common elastomers
9.1 Regular solutions of simple non-electrolytes
9.3 Mean-field lattice theory for polymers (Flory-Huggins model)
9.3.1 Free energy of mixing
9.4 Experimental behavior of polymer solutions and the Flory-Huggins model
9.4.1 Solvent activity in concentrated solutions
9.4.2 Solubility and critical solution temperatures
9.4.3 Lower critical solution temperatures
9.4.4 Dilute solutions, the second virial coefficient
9.5 The semi-dilute regime
9.5.1 Overlap concentration in good solvents
9.5.2 Osmotic pressure in the semi-dilute region
9.5.3 The correlation length
9.6.1 The two-parameter model
9.6.3 Second virial coefficient
9.7 Equation-of-state theories
9.7.1 Equations of state for pure fluids
9.7.2 Application to solutions
9.7.3 Comparison with experiment
9.8 More rigorous extensions of theory
Appendix A9.1 Entropy and energy of mixing of equal-sized molecules on a lattice
Appendix A9.2 Entropy of polymer chains on a lattice
Appendix A9.3 Cell models for monatomic fluids
The Science of Polymer Molecules
( Cambridge Solid State Science Series )
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