With the global renewal of interest in PVC, this book is well timed, considering that PVC stabilization is the most important aspect of its formulation and performance. Only four books have been published on PVC degradation and stabilization (the last one in the 1980s), and two of them are by the author of this book.

Separate chapters review information on chemical structure, PVC manufacturing technology, morphology, degradation by thermal energy, and UV, gamma, and other forms of radiation, mechanodegradation, chemical degradation, analytic methods used in studying of degradative and stabilization processes, stabilization, and effect of PVC and its additives on health, safety and environment.

This book contains analysis of all essential papers published until recently on the above subject. It either locates the answers to relevant questions and offers solutions or gives references in which such answers can be found.

PVC Degradation and Stabilization is must have for chemists, engineers, scientists, university teachers and students, designers, material scientists, environmental chemists, and lawyers who work with polyvinyl chloride and its additives or have any interest in these products. This book is the one authoritative source on the subject.

Preface
PVC has a long history of development which began nearly 100 years ago with the patenting of the concepts of emulsion and suspension polymerization, the development of the industrial process of vinyl chloride synthesis, and patents on its plasticization, followed by the development of stabilization about 75 years ago. PVC has known rapid growth to utmost prominence and dramatic downfall almost to elimination, and it finally has regained a deserved, second position among commercial polymers.PVC owes both its prominence and its downfall to research: meticulous, cutting-edge studies and unscrupulous bad science which stops progress and derails achievements.
PVC degradation during processing and use was always one of the most essential elements of PVC science and technology. Many approaches to stabilization changed and some groups of stabilizers are not used in new production. This book was written to show new trends and directions. It also contains clearly indicated information about past stabilizers, which is needed in order to understand the principles of stabilization and effective recycling.
For me, it has been an interesting experience to actively participate in the growth of this branch of science and summarize its achievements and the directions which it faces now, here and in my two previous books, written 25 years ago. I hope the clarity and completeness of the description of research findings as we know them today will help in further research and, most importantly, lead to successful and responsible practical applications of additives in PVC processing and applications.

George Wypych
Toronto, May 8, 2008


1. Chemical Structure of PVC
1.1 Repeat structures and their basic organic chemistry
1.1.1 Bronsted acid source with controllable emission
1.2 Molecular weight and its distribution
1.2.1 Kuhn-Mark-Houwink-Sakurada
1.2.2 Fikentscher K number
1.2.3 Chain length
1.3 Prediction of formation of irregular segments
1.3.1 Ab initio
1.3.2 Monte Carlo
1.4 Irregular segments
1.4.1 Branches
1.4.2 Tertiary chlorine
1.4.3 Unsaturations
1.4.4 Oxygen containing groups
1.4.4.1 Ketochloroallyl groups
1.4.4.2 a- and b-carbonyl groups
1.4.5 Head-to-head structures
1.4.5 Initiator rests
1.4.6 Transfer agent rests
1.4.8 Defects introduced during processing
1.4.9 PVC having increased stability
References

2. PVC Manufacture Technology
2.1 Monomer
2.2 Basic Steps of Radical Polymerization
2.2.1 Initiation
2.2.2 Propagation
2.2.3 Termination
2.2.4 Chain transfer to monomer
2.3 Polymerization technology
2.3.1 Suspension
2.3.2 Paste resin manufacturing processes
2.3.3 Bulk
2.3.4 Solution
2.4 Polymerization conditions and PVC properties
References

3. PVC Morphology
3.1. Molecular weight of polymer (chain length)
3.2. Configuration and conformation
3.3. Chain folds
3.4. Chain thickness
3.5 Entanglements
3.6 Crystalline structure
3.7 Grain morphology
3.7.1 Stages of morphology development during manufacture
3.7.1.1 Suspension polymerization
3.7.1.2 Paste grades manufacture
3.7.1.3 Bulk polymerization
3.7.2 Effect of morphology on degradation
References

4. Principles of Thermal Degradation
4.1 The reasons for polymer instability
4.1.1 Structural defects
4.1.1.1 Branches
4.1.1.2 Tertiary chlorine
4.1.1.3 Unstaturations
4.1.1.4 Oxygen containing groups
4.1.1.5 Head-to-head structures
4.1.1.6 Morphology
4.1.2 Polymerization residue
4.1.2.1 Initiator rests
4.1.2.2 Transfer agent rests
4.1.2.3 Polymerization additives
4.1.3 Metal derivatives
4.1.3.1 Metal chlorides
4.1.3.2 Copper and its oxide
4.1.4 Hydrogen chloride 14
4.1.5 Impurities
4.1.6 Shear
4.1.7 Temperature
4.1.8 Surrounding atmosphere
4.1.9 Additives
4.2 Mechanisms of thermal degradation
4.2.1 Molecular mechanism
4.2.2 Amer-Shapiro mechanism
4.2.3 Six-center concerted mechanism
4.2.4 Activation enthalpy
4.2.5 Radical-chain theory
4.2.6 Ionic
4.2.7 Polaron
4.2.8 Degenerated branching
4.2.9 Transition state theory
4.2.10 Recapitulation
4.3 Kinetics
4.3.1 Initiation
4.3.2 Propagation
4.3.3 Termination
4.4 Results of thermal degradation
4.4.1 Volatiles
4.4.2 Weight loss
4.4.3 Char formation
4.4.4 Ash content
4.4.5 Thermal lifetime
4.4.6 Optical properties
4.4.6.1 Color change
4.4.6.2 Extinction coefficient
4.4.6.3 Absorbance
4.4.7 Molecular weight
4.4.8 Mechanical properties
4.4.9 Electric properties
4.5 Effect of additives
4.5.1 Blend polymers
4.5.1.1 ABS
4.5.1.2 Chlorinated polyethylene, CPE
4.5.1.3 Epoxidized butadiene/styrene block copolymer
4.5.1.4 Epoxidized natural rubber
4.5.1.5 Ethylene vinyl acetate, EVA
4.5.1.6 High impact polystyrene, HIPS
4.5.1.7 Methylmethacrylate-butadiene-styrene
4.5.1.8 Nitrile rubber, NBR
4.5.1.9 Oxidized polyethylene, OPE
4.5.1.10 Polyacrylate
4.5.1.11 Polyacrylonitrile
4.5.1.12 Polyamide
4.5.1.13 Polyaniline, PANI
4.5.1.13 Polycarbonate, PC
4.5.1.14 Polyethylene, PE
4.5.1.15 Poly(methyl methacrylate), PMMA
4.5.1.16 Poly(N-vinyl-2-pyrrolidone), PVP
4.5.1.17 Polysiloxane
4.5.1.18 Polystyrene, PS
4.5.1.19 Polythiophene