Author: George Wypych
Published: 2008 - Second edition
Pages: 400
Figures: 300
Tables: 35
ISBN: 978-1-895198-39-3
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.
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
4.5.1.20 Polyurethane
4.5.1.21 Poly(vinyl acetate), PVAc
4.5.1.22 Poly(vinyl alcohol), PVA
4.5.1.23 Poly(vinyl butyral), PVB
4.5.1.24 SAN
4.5.2 Antiblocking
4.5.3 Antistatics agents
4.5.4 Biocides and fungicides
4.5.5 Blowing agents
4.5.6 Fillers
4.5.7 Flame retardants
4.5.8 Impact modifiers
4.5.9 Lubricants
4.5.10 Pigments
4.5.11 Plasticizers
4.5.12 Process aids
4.5.13 Solvents
4.5.14 Stabilizers
References
5 Principles of UV Degradation
5.1 Reasons for polymer instability
5.1.1 Radiative energy
5.1.2 Radiation intensity
5.1.3 Radiation incidence
5.1.4 Absorption of radiation by materials
5.1.5 Bond structure
5.1.6 Thermal history
5.1.7 Photosensitizers
5.1.8 Wavelength sensitivity
5.1.9 Thermal variability
5.1.10 Pollutants
5.1.11 Laboratory degradation conditions
5.2 Mechanisms of degradation
5.2.1 Radical mechanism
5.2.1.1 Photooxidation mechanism
5.2.1.2 Mechanistic scheme
5.2.1.3 Conformational mechanism
5.2.1.4 Electronic-to-vibrational energy transfer
5.2.1.5 Other contributions to the mechanism of photodegradation
5.3 Kinetics
5.3.1 Initiation
5.3.2 Propagation
5.3.3 Termination
5.4 Results of UV degradation
5.4.1 Photodiscoloration
5.4.2 Mechanical properties
5.4.3 Other properties
5.5 Effect of additives
5.5.1 Biocides and fungicides
5.5.2 Fillers
5.5.3 Flame retardants
5.5.4 Impact modifiers
5.5.5 Lubricants
5.5.6 Pigments and colorants
5.5.6.1 Titanium dioxide
5.5.6.2 Zinc oxide
5.5.6.3 Iron-containing pigments
5.5.7 Plasticizers
5.5.8 Polymer blends
5.5.9 Solvents
5.5.10 Stabilizers
References
6 Principles of Degradation by γ-Radiation
6.1 The reasons for polymer instability
6.2 Mechanisms
6.3 Kinetics
6.4 Results
6.5 Effect of additives
6.5.1 Plasticizers
6.5.2 Fillers
6.5.3 Stabilizers
References
7 Degradation by Other Forms of Radiation
7.1 Argon plasma
7.2 b-radiation (electron beam)
7.3 Corona discharge
7.4 Ion (proton) beam
7.5 Laser
7.6 Metallization
7.7 Microwave
7.8 Neutron irradiation
7.9 Oxygen plasma
7.10 X-rays
7.11 Ultrasonic
References
8 Mechanodegradation
References
9 Chemical Degradation
9.1 methods of chemical dehydrochlorination
9.2. Kinetics and mechanisms of reaction
References
10 Analytical Methods
10.1 Heat stability test
10.1.1 Sample preparation
10.1.2 Kinetic studies of dehydrochlorination
10.1.3 Dehydrochlorination rate and optical changes
10.1.4 Degradation in solution
10.2 Thermogravimetric analysis
10.2.1 Differential scanning calorimetry, DSC
10.2.2 Mass loss
10.3 Combustion
10.4 Optical properties
10.5 Spectroscopic methods
10.5.1 Atomic absorption, AAS
10.5.2 Auger
10.5.3 Electron spin resonance, ESR
10.5.4 Fourier transform infrared, FTIR
10.5.5 Laser photopyroelectric effect spectrometry
10.5.6 Mass, MS
10.5.7 Mossbauer
10.5.8 Near infrared, NIR
10.5.9 Nuclear magnetic resonance, NMR
10.5.10 Positron annihilation lifetime spectroscopy, PAS
10.5.11 Raman
10.5.12 Time-of-flight secondary ion mass spectrometry, ToF-SIMS
10.5.13 X-ray analysis
10.5.13.1 Small angle light scattering, SAXS
10.5.13.2 Wide angle light scattering, WAXS or WAXD
10.5.14 X-ray photoelectron spectroscopy, XPS
10.5.15 UV-visible
10.6 Chromatographic methods
10.1 Gas chromatography
10.6.2 Liquid chromatography
10.7 Mechanical properties
10.8 Other essential methods of testing
10.8.1 Action spectrum
10.8.2 Coulter counter
10.8.3 Gel content
10.8.4 Ozonolysis
10.8.5 Peroxide titration
10.8.6 Rheological studies
10.9 International standards
References
11 Principles of PVC stabilization
The details of this chapter will be announced later
12 Health and safety and environmental impact
12.1 Toxic substance control
12.2. Carcinogenic effect
12.3 Teratogenic and mutagenic effect
12.4 Workplace exposure limits
12.5 Exposure from consumer products
12.6 Drinking water
12.7 Food regulatory acts
12.8 Toxicity of stabilizers
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