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Reactive Polymers:
Fundamentals and
Applications
A Concise Guide to Industrial Polymers
Third Edition
Johannes Karl Fink

REACTIVE POLYMERS:
FUNDAMENTALS AND
APPLICATIONS
PLASTICS DESIGN LIBRARY (PDL)
PDL HANDBOOK SERIES
Series Editor: Sina Ebnesajjad, PhD (sina@FluoroConsultants.com)

President, FluoroConsultants Group, LLC
Chadds Ford, PA, USA
www.FluoroConsultants.com
The PDL Handbook Series is aimed at a wide range of engineers and other professionals working in the plastics industry, and
related sectors using plastics and adhesives.
PDL is a series of data books, reference works and practical guides covering plastics engineering, applications, processing, and
manufacturing, and applied aspects of polymer science, elastomers and adhesives.
Recent titles in the series

Biopolymers: Processing and Products, Michael Niaounakis (ISBN: 9780323266987)
Biopolymers: Reuse, Recycling, and Disposal, Michael Niaounakis (ISBN: 9781455731459)
Carbon Nanotube Reinforced Composites, Marcio Loos (ISBN: 9781455731954)
Extrusion, 2e, John Wagner & Eldridge Mount (ISBN: 9781437734812)
Fluoroplastics, Volume 1, 2e, Sina Ebnesajjad (ISBN: 9781455731992)
Handbook of Biopolymers and Biodegradable Plastics, Sina Ebnesajjad (ISBN: 9781455728343)
Handbook of Molded Part Shrinkage and Warpage, Jerry Fischer (ISBN: 9781455725977)
Handbook of Polymer Applications in Medicine and Medical Devices, Kayvon Modjarrad & Sina Ebnesajjad (ISBN:
9780323228053)
Handbook of Thermoplastic Elastomers, Jiri G. Drobny (ISBN: 9780323221368)
Handbook of Thermoset Plastics, 2e, Hanna Dodiuk & Sidney Goodman (ISBN: 9781455731077)
High Performance Polymers, 2e, Johannes Karl Fink (ISBN: 9780323312226)
Introduction to Fluoropolymers, Sina Ebnesajjad (ISBN: 9781455774425)
Ionizing Radiation and Polymers, Jiri G. Drobny (ISBN: 9781455778812)
Manufacturing Flexible Packaging, Thomas Dunn (ISBN: 9780323264365)
Plastic Films in Food Packaging, Sina Ebnesajjad (ISBN: 9781455731121)
Plastics in Medical Devices, 2e, Vinny Sastri (ISBN: 9781455732012)
Polylactic Acid, Rahmat et. al. (ISBN: 9781437744590)
Polyvinyl Fluoride, Sina Ebnesajjad (ISBN: 9781455778850)
Reactive Polymers, 2e, Johannes Karl Fink (ISBN: 9781455731497)
The Effect of Creep and Other Time Related Factors on Plastics and Elastomers, 3e, Laurence McKeen (ISBN: 9780323353137)
The Effect of Long Term Thermal Exposure on Plastics and Elastomers, Laurence McKeen (ISBN: 9780323221085)
The Effect of Sterilization on Plastics and Elastomers, 3e, Laurence McKeen (ISBN: 9781455725984)
The Effect of Temperature and Other Factors on Plastics and Elastomers, 3e, Laurence McKeen (ISBN: 9780323310161)
The Effect of UV Light and Weather on Plastics and Elastomers, 3e, Laurence McKeen (ISBN: 9781455728510)
Thermoforming of Single and Multilayer Laminates, Ali Ashter (ISBN: 9781455731725)
Thermoplastics and Thermoplastic Composites, 2e, Michel Biron (ISBN: 9781455778980)
Thermosets and Composites, 2e, Michel Biron (ISBN: 9781455731244)
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REACTIVE POLYMERS:
FUNDAMENTALS AND
APPLICATIONS
A CONCISE GUIDE TO
INDUSTRIAL POLYMERS
Third Edition
Johannes Karl Fink

Montanuniversität Leoben, Austria
AMSTERDAM • BOSTON • HEIDELBERG • LONDON

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SAN FRANCISCO • SINGAPORE • SYDNEY • TOKYO
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First edition 2005
Second edition 2013
Third edition 2018
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This book and the individual contributions contained in it are protected under copyright by the Publisher (other than as may be noted herein).
Notices
Knowledge and best practice in this field are constantly changing. As new research and experience broaden our understanding, changes in research methods,
professional practices, or medical treatment may become necessary.
Practitioners and researchers must always rely on their own experience and knowledge in evaluating and using any information, methods, compounds, or
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they have a professional responsibility.
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Publisher: Matthew Deans

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Typeset by VTeX
Contents
Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xxiii
1. Unsaturated Polyester Resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1

1.1 History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 Monomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2.1 Monomers for an Unsaturated Polyester . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2.2 Vinyl Monomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.2.3 Specialities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.2.4 Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
1.2.5 Manufacture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
1.3 Special Additives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
1.3.1 Inhibitors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
1.3.2 Thickeners . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
1.3.3 Emission Suppressants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
1.3.4 Fillers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
1.3.5 Reinforcing Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
1.3.6 Additives for Molding Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
1.3.7 Low-Profile Additives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
1.3.8 Interpenetrating Polymer Networks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
1.3.9 Poly(urethane) Hybrid Networks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
1.3.10 Flame Retardants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
1.3.11 Production Data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
1.4 Curing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
1.4.1 Initiator Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
1.4.2 Low Temperature Curing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
1.4.3 Promoters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
1.4.4 Initiator Promoter Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
1.4.5 Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
1.5 Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
1.5.1 Structure Properties Relationships . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
1.5.2 Hydrolytic Stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
1.5.3 Recycling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
1.6 Applications and Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
1.6.1 Decorative Specimens . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
1.6.2 Polyester Concrete . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
1.6.3 Reinforced Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
1.6.4 Pre-accelerated Resin Compositions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
1.6.5 Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
1.6.6 Medical Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
1.7 Special Formulations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
1.7.1 Vinyl Ester Resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
1.7.2 Electrically Conductive Resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
1.7.3 Poly(ε-caprolactone)-perfluoropolyether Copolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
1.7.4 Toner Compositions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
1.7.5 Pour Point Depressants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
1.7.6 Biodegradable Polyesters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
1.7.7 Neutron Shielding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
1.7.8 Bone Cement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
1.7.9 Compatibilizers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
1.7.10 Reactive Melt Modification of Poly(propylene) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
v
vi Contents
1.7.11 Encapsulation of Electric and Electronic Parts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49

1.7.12 Lamp Reflector . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
1.7.13 LED Reflector . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
1.7.14 Toner Resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
2. Poly(urethane)s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
2.1 History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
2.2 Monomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
2.2.1 Diisocyanates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
2.2.2 Polyols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
2.2.3 Other Polyols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
2.2.4 Polyamines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
2.2.5 Chain Extenders . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
2.2.6 Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
2.2.7 Blowing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
2.3.1 Fillers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
2.4 Curing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
2.4.1 Recycling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
2.5 Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
2.5.1 Mechanical Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
2.5.2 Thermal Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
2.5.3 Weathering Resistance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
2.6.1 Casting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
2.6.2 Foams . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
2.6.3 Membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100
2.6.4 Passive Air Samplers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
2.6.5 Identification Tagging . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
2.7.1 Interpenetrating Networks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102
2.7.2 Methacrylate Copolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
2.7.3 Grafting with Isocyanates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
2.7.4 Composites for Thermal Energy Storage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
2.7.5 Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
2.7.6 Medical Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
2.7.7 Solid State Fermentation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112
2.7.8 Catalysis of the Knoevenagel Reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112
2.7.9 Oil Spill Cleanup . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112
2.7.10 Biofiltration of Organic Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113
2.7.11 Footwear . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
2.7.12 Waterborne Poly(urethane)s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
2.7.13 Elastic Conductive Filaments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
2.7.14 Non-Isocyanate Poly(urethane) Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
2.7.15 Biobased Networks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116
2.7.16 Stamps . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116
2.7.17 Nanowire Electrodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
2.7.18 Electromagnetic Interference Shielding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118
2.7.19 Electrically Conductive Adhesives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118
2.7.20 Ceramic Foams . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118
Contents vii
2.7.21 Adhesion Modification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119

2.7.22 Electrolytes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119
2.7.23 3 D Printing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120
3. Epoxy Resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 139

3.1 History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 139
3.2 Monomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 139
3.2.1 Epoxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 139
3.2.2 Phenols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 140
3.2.3 Specialities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 142
3.2.4 Manufacture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 147
3.3.1 Crosslinking Agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
3.3.2 Toughening Agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
3.3.3 Antiplasticizers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155
3.3.4 Lubricants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155
3.3.5 Adhesion Improvers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 156
3.3.6 Conductivity Modifiers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 156
3.3.7 Accelerators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 156
3.3.9 Graphene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 160
3.3.10 Interpenetrating Polymer Networks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 160
3.3.11 Organic and Inorganic Hybrids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 162
3.3.13 Corrosion Inhibitor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 167
3.3.14 Production Data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 167
3.4 Curing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 168
3.4.2 Compounds with Activated Hydrogen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 168
3.4.3 Coordination Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 173
3.4.4 Ionic Curing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 173
3.4.5 Photoinitiators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 176
3.4.6 Derivatives of Michler’s Ketone . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 177
3.4.7 Epoxy Systems with Vinyl Groups . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 179
3.4.8 Thiol-Epoxy Click Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 179
3.4.9 Halogen-Free Flame Retardant Co-curing Agent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 179
3.4.10 Curing Kinetics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 179
3.4.11 Thermal Curing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 181
3.4.12 Microwave Curing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 182
3.5 Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 182
3.5.1 Hybrid Polymers and Mixed Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 183
3.5.2 Water Absorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 183
3.5.3 Cryogenic Mechanical Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 184
3.5.4 Recycling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 184
3.6.1 Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 186
3.6.2 Foams . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 187
3.6.3 Adhesives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 187
3.6.4 Uses for Cement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 187
3.6.5 Molding Techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 189
3.6.6 Stabilizers for Poly(vinyl chloride) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 189
viii Contents
3.7.1 Development of Formulations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 189

3.7.2 Restoration Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 189
3.7.3 Epoxy Polymer Concrete . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 189
3.7.4 Biodegradable Epoxy-Polyester Resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 190
3.7.5 Swellable Epoxies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 190
3.7.6 Fiber-Reinforced Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 190
3.7.7 Membrane Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 191
3.7.8 Controlled-Release Formulations for Agriculture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 191
3.7.9 Shape Memory Composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 191
3.7.10 Electronic Packaging Application . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 191
3.7.11 Ion Selective Electrodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 192
3.7.12 Solid Polymer Electrolytes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 192
3.7.13 Optical Resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 192
3.7.14 Reactive Solvents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195
3.7.15 Encapsulated Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 196
3.7.16 Functionalized Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 196
3.7.17 Epoxy Resins as Compatibilizers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 196
3.7.18 Surface Metallization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 198
3.7.19 Self-Healing Epoxy Resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 198
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 199
4. Phenol/Formaldehyde Resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 225

4.1 History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 225
4.2 Monomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 225
4.2.1 Phenol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 226
4.2.2 o-Cresol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 226
4.2.3 Cardanol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 226
4.2.4 Formaldehyde . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 227
4.2.5 Multihydroxymethylketones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 227
4.2.6 Production Data of Important Monomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 227
4.2.7 Basic Resin Types . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 227
4.2.8 Specialities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 229
4.2.9 Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 230
4.2.10 Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 231
4.2.11 Manufacture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 233
4.3.1 Low Emission Types . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 233
4.3.2 Boric Acid Modified Types . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 235
4.3.3 Fillers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 235
4.4 Curing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 236
4.4.1 Model Studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 236
4.4.2 Experimental Design . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 237
4.4.3 Water Content . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 237
4.4.4 Influence of Pressure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 237
4.4.5 Wood . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 237
4.4.6 Novolac Curing Agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 238
4.4.7 Resol Resin Hardeners . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 239
4.4.8 Triacetin and Urea . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 239
4.4.9 Ester-Type Accelerators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 239
4.4.10 Ashless Resol Resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 239
4.5 Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 240
4.5.1 Mechanical Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 240
Contents ix

4.5.3 Recycling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 240
4.6.1 Binders for Glass Fibers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 241
4.6.2 Molding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 242
4.6.3 Novolac Photoresists . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 242
4.6.4 High-Temperature Adhesives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 242
4.6.5 Urethane-Modified Types . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 242
4.6.6 Carbon Products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 242
4.7.1 Chemical Resistant Types . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 244
4.7.2 Ion Exchange Resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 245
4.7.3 Ionic Liquids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 245
4.7.4 Brakes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 245
4.7.5 Soft Magnetic Composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 245
4.7.6 Waterborne Types . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 245
4.7.7 High-Viscosity Novolac . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 245
4.7.8 Foams . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 245
4.7.9 Visbreaking of Petroleum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 246
4.7.10 Resorcinol for Foam Production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 246
4.7.11 Archaeological Wood . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 246
4.8 Testing Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 246
4.8.1 Water Tolerance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 246
4.8.2 Salt Tolerance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 247
4.8.3 Free Phenol Content . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 247
4.8.4 Free Formaldehyde . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 247
4.8.5 pH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 247
4.8.6 Solids Content . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 247
4.8.7 o-Cresol Contact Allergy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 247
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 247
5. Urea/Formaldehyde Resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 255

5.1 History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 255
5.2 Synthesis of Resin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 255
5.2.1 Formaldehyde . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 255
5.2.2 Urea . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 255
5.2.3 Ammonia . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 255
5.2.4 Diketones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 255
5.2.5 Glyoxal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 255
5.2.6 Dimethoxy Ethanal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 256
5.2.7 Specialities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 256
5.2.8 Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 258
5.2.9 Manufacture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 259
5.3.1 Modifiers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 259
5.3.2 Fillers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 260
5.3.4 Production Data of Important Monomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 262
5.4 Curing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 262
5.5 Measurement of Curing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 263
5.6 Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 263
5.6.1 Formaldehyde Release . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 263
5.6.2 Storage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 264
x Contents
5.6.3 Hydrolytic Stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 264

5.6.4 Crystallinity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 264
5.7.1 Glue Resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 265
5.7.2 Bonding of Recycled Wood Fibers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 265
5.7.3 Binders . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 265
5.7.4 Emulsion Paints . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 265
5.7.5 Foundry Sands . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 266
5.7.6 Electrical Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 266
5.7.7 Formation of Nano Powders . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 266
5.7.8 Waste Water Cleaning . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 267
5.8.1 Ready-Use Powders . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 267
5.8.2 Cyclic Urea Prepolymer in PF Laminating Resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 267
5.8.3 Liquid Fertilizer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 267
5.8.4 Soil Amendment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 267
5.8.5 Microencapsulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 267
5.8.6 Degradable Seedling Containers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 268
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 269
6. Melamine Resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 275

6.1 History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 275
6.2 Monomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 275
6.2.1 Melamine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 275
6.2.2 Other Modifiers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 275
6.2.3 Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 275
6.2.4 Manufacture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 276
6.3.3 Thermo-Oxidative Decomposition of Sapwood . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 277
6.3.4 Recycling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 277
6.4 Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 278
6.4.1 Thermal Degradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 278
6.5.1 Wood Impregnation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 279
6.5.2 Waste Water Cleaning . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 279
6.5.3 Windrow Composting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 279
6.5.4 Separation of Metal Ions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 280
6.6.1 Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 280
6.6.2 Encapsulated Dyes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 281
6.6.3 Porous Resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 281
6.6.4 Resins with Increased Elasticity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 282
6.6.5 Microspheres . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 282
6.6.6 Supercapacitors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 282
6.6.7 Porous Activated Carbons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 282
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 282
7. Furan Resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 287

7.1 History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 287
7.2 Monomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 287
7.2.1 Furfural . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 287
Contents xi
7.2.2 Furfuryl Alcohol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 287

7.2.3 Specialities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 288
7.2.4 Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 288
7.4 Curing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 289
7.4.1 Acidic Curing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 289
7.4.2 Oxidative Curing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 290
7.4.3 Ultrasonic Curing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 290
7.4.4 Microwave Curing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 290
7.5 Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 290
7.5.1 Recycling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 290
7.5.2 Flame Retardancy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 290
7.6.1 Carbons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 291
7.6.2 Chromatography Support . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 293
7.6.3 Composite Carbon Fiber Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 293
7.6.4 Protective Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 294
7.6.5 Foundry Binders . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 294
7.6.6 Glass Fiber Binders . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 295
7.6.7 Aluminum Electrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 295
7.6.8 Panels and Fiberboards . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 295
7.6.9 Oil Field Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 295
7.6.10 Molding Sands . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 296
7.6.11 Photosensitive Polymer Electrolytes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 297
7.6.12 Plant Growth Substrates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 297
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 297
8. Silicones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 303
8.1 History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 303
8.2 Monomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 303
8.2.1 Chlorosilanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 303
8.2.2 Silsesquioxanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 303
8.2.3 Hydrogen-Silsesquioxane Resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 304
8.2.4 Alkoxysiloxanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 304
8.2.5 Silphenylenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 305
8.2.6 Epoxy-Modified Siloxanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 305
8.2.7 Silaferrocenophanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 305
8.2.8 Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 305
8.2.9 Manufacture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 307
8.3 Modified Types . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 307
8.3.1 Chemical Modifications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 307
8.3.2 Fillers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 308
8.4 Curing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 309
8.4.1 Curing by Condensation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 309
8.5 Crosslinking . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 310
8.5.1 Condensation Crosslinking . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 310
8.5.2 Peroxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 310
8.5.3 Hydrosilylation Crosslinking . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 310
8.6 Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 311
8.6.1 Silicone Rubber . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 311
xii Contents

8.6.3 Electrical Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 312
8.6.4 Surface Tension Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 312
8.6.5 Antioxidants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 312
8.6.6 Gas Permeability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 312
8.6.7 Weathering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 312
8.7.1 Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 313
8.7.2 Adhesives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 314
8.7.3 Antifoaming Agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 314
8.7.4 Release Agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 314
8.7.5 Sealing and Jointing Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 315
8.7.6 Bioceramics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 315
8.7.7 Electrical Industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 315
8.7.8 Medical Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 317
8.8.1 Polyimide Resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 317
8.8.2 Thermal Transfer Ribbons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 318
8.8.3 Self-Assembly Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 318
8.8.4 Plasma Grafting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 318
8.8.5 Antifouling Compositions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 318
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 319
9. Acrylic Resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 325

9.1 History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 325
9.2 Monomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 325
9.2.1 Specialities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 325
9.2.2 Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 327
9.2.3 Manufacture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 327
9.3.1 Ultraviolet Absorbers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 327
9.4 Curing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 329
9.4.2 Promoters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 329
9.4.3 Two-Photon Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 329
9.5 Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 330
9.5.1 Electrical Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 330
9.5.2 Hydrolytic and Photochemical Stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 330
9.5.3 Recycling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 330
9.5.4 Pyrolysis Chromatography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 330
9.6.1 Acrylic Premixes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 331
9.6.2 Epoxy Acrylates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 331
9.6.3 Urethane Acrylates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 332
9.6.4 High-Performance Biocomposite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 332
9.6.5 Solid Polymer Electrolytes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 332
9.7.1 Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 333
9.7.2 Tackifier Resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 336
9.7.3 Concrete . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 336
9.7.4 Ionomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 336
9.7.5 Porous Superabsorbent Resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 336
Contents xiii
9.7.6 Drug Release Membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 336

9.7.7 Support Materials for Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 336
9.7.8 Electron Microscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 337
9.7.9 Stereolithography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 337
9.7.10 Electronic Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 337
9.7.11 Magnetic Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 337
9.7.12 Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 337
9.7.13 Waste Water Treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 338
9.7.14 Laminated Films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 338
9.7.15 Ink-Jet Printing Media . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 339
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 339
10. Cyanate Ester Resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 345

10.1 History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 345
10.2 Monomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 345
10.2.1 Specialities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 345
10.2.2 Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 346
10.3 Special Additives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 347
10.3.1 Fillers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 347
10.3.2 Flame Retardants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 348
10.4 Curing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 349
10.4.1 Thermal Curing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 349
10.4.2 Curing with Epoxy Groups . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 352
10.4.3 Curing with Unsaturated Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 352
10.4.4 Organo-Gelation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 353
10.5 Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 354
10.5.1 Modeling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 354
10.5.2 Thermal Stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 354
10.5.3 Hydrolytic Degradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 355
10.6 Applications and Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 355
10.6.1 Fiber Composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 355
10.6.2 Electronic Industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 355
10.6.3 Spacecraft . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 356
10.7 Special Formulations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 356
10.7.1 Phenolic Triazine Compositions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 356
10.7.2 Epoxy Containing Compositions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 356
10.7.3 Bismaleimide Triazine Resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 357
10.7.4 Siloxane Crosslinked Resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 358
10.7.5 Nanoporous Compositions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 358
10.7.6 Alloys with Thermoplastics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 359
10.7.7 Coupling Agents for Cyanate Ester Resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 360
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 360
11. Bismaleimide Resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 367

11.1 Monomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 367
11.1.1 4,4 -Bis(maleimido)diphenylmethane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 367
11.1.2 Allyl Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 367
11.1.3 Poly(ethylene glycol) End-Capped with Maleimide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 369
11.1.4 Poly(phenylene oxide) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 369
11.1.5 Phenyl Polysiloxane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 369
11.1.6 Bismaleimide Bisimides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 369
11.1.7 Maleimide Silicone Monomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 369
xiv Contents
11.1.8 Maleimide Epoxy Monomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 370

11.1.9 Phosphorus-Containing Monomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 370
11.1.10 Fluorene Cardo Based Monomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 371
11.1.11 Multiring Monomers with Pendant Chains . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 371
11.1.12 Benzoxine Comonomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 373
11.1.13 Reactions of Maleimides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 374
11.1.14 Specialities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 376
11.2.1 Tougheners and Modifiers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 379
11.2.2 Fillers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 382
11.2.3 Titanium Dioxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 383
11.2.5 Flame Retardants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 384
11.3 Curing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 385
11.3.1 Monitoring Curing Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 385
11.3.2 Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 385
11.3.3 Interpenetrating Networks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 388
11.4 Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 388
11.4.1 Thermal Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 388
11.4.2 Water Sorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 389
11.4.3 Tribological Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 389
11.4.4 Recycling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 390
11.5.1 Biochemical Reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 390
11.6.1 Adhesives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 390
11.6.2 Resin Transfer Molding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 391
11.6.3 Polyquinoline Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 391
11.6.4 Phosphazene-Triazine Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 391
11.6.5 Porous Networks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 391
11.6.6 Nonlinear Optical Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 391
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 392
12. Terpene Resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 403

12.1 History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 403
12.2 Monomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 403
12.2.1 Resin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 404
12.2.2 Turpentine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 404
12.2.3 Rosin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 404
12.3 Curing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 404
12.3.1 Homopolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 404
12.3.2 Copolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 405
12.3.3 Terpene Phenolic Resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 405
12.3.4 Terpene Maleimide Resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 406
12.3.5 Poly(farnesene)s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 406
12.4 Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 407
12.4.1 Solubility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 407
12.4.2 Adhesive Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 408
12.4.3 Characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 408
12.4.4 Recycling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 408
12.5.1 Sealants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 409
12.5.2 Pressure-Sensitive Adhesives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 409
Contents xv
12.5.3 Polyacrylate Hot-Melt Pressure-Sensitive Adhesives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 410

12.5.4 Hot-Melt Adhesives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 410
12.5.5 Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 411
12.5.6 Sizing Agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 411
12.5.7 Toner Compositions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 412
12.5.8 Chewing Gums . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 412
12.5.9 Tire Puncture Sealant . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 413
12.6.1 Toughener for Novolacs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 413
12.6.2 Fluoro Copolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 413
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 413
13. Cyanoacrylates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 417

13.1 Monomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 417
13.1.1 Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 417
13.1.2 Crosslinkers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 418
13.1.3 Commercial Products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 418
13.2.1 Plasticizers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 419
13.2.2 Accelerators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 419
13.2.3 Thickeners . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 421
13.2.4 Stabilizers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 421
13.2.5 Primers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 422
13.2.6 Diazabicyclo and Triazabicyclo Primers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 422
13.2.7 Polyamine Dendrimers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 423
13.3 Curing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 423
13.3.1 Photo Curing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 424
13.4 Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 424
13.4.1 Adhesion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 424
13.5.1 Rapid Prototyping . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 425
13.5.2 High Resolution Lithography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 425
13.5.3 Cosmetic and Medical Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 425
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 429
14. Benzocyclobutene Resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 433

14.1 Modified Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 435
14.1.1 Thermotropic Copolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 435
14.1.2 BCB-Modified Aromatic Polyamides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 435
14.1.3 BCB End-Capped Polyimides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 436
14.1.4 BCB Carbosilane Thermosets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 436
14.1.5 BCB Modified Poly(siloxane) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 437
14.1.6 BCB modified Poly(silmethylene) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 437
14.1.7 Flame Resistant Formulations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 437
14.2 Crosslinkers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 437
14.2.1 Modified Poly(ethylene terephthalate) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 437
14.2.2 Thermally Induced Crosslinking . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 437
14.2.3 Ring Functionalization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 438
14.3 Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 438
14.3.1 Mechanical Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 438
14.3.2 Reactive Ion Etching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 439
14.4.1 Applications in Microelectronics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 439
xvi Contents
14.4.2 Optical Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 441

14.4.3 Electrical Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 443
14.4.4 Shape-Memory Compositions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 444
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 444
15. Reactive Extrusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 449

15.1 Extruder . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 449
15.1.1 Heat of Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 452
15.1.2 Ceiling Temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 452
15.1.3 Strategy of Reactive Extrusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 452
15.2 Compositions of Industrial Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 453
15.2.1 Polyolefins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 453
15.2.2 Poly(styrene) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 458
15.2.3 Poly(styrene) Poly(propylene) Blends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 459
15.2.4 Poly(oxymethylene) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 460
15.2.5 Poly(tetramethylene ether) and Poly(caprolactam) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 460
15.2.6 Polyamides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 460
15.2.7 Poly(butyl methacrylate) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 461
15.2.8 Poly(carbonate) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 461
15.2.9 Polyesters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 464
15.2.10 Thermoplastic Poly(urethane) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 464
15.2.11 PVDF Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 465
15.3 Biodegradable Compositions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 465
15.3.1 Biodegradable Polyesters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 466
15.3.2 Compatibility Improvement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 467
15.3.3 Lignin Grafted Hydroxybutyrate Copolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 467
15.3.4 Nanoclay Grafted Hydroxybutyrate Copolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 467
15.3.5 Poly(lactide)s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 467
15.3.6 Starch and Cellulose Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 474
15.3.7 Modification of Wood Waste . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 477
15.3.8 Biodegradable Fibers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 477
15.3.9 Poly(ε-caprolactone) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 477
15.3.10 Cationically Modified Starch . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 478
15.3.11 Blends of Starch and Polyesters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 479
15.3.12 Blends of Starch and Poly(acrylamide) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 480
15.3.13 Blends of Chitosan and Poly(acrylic acid) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 480
15.3.14 Poly(butylene succinate) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 481
15.3.15 Blends of Protein and Polyester . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 481
15.3.16 Modification of Protein with Monomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 481
15.3.17 Enzyme-Catalyzed Polyester Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 481
15.4 Chain Extenders . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 482
15.4.1 Recycling of Poly(ethylene terephthalate) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 482
15.4.2 Foamable Poly(ethylene terephthalate) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 482
15.4.3 Modified Poly(ethylene terephthalate) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 482
15.4.4 Poly(butylene terephthalate) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 483
15.5 Related Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 483
15.5.1 Transesterification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 483
15.5.2 Hydrolysis and Alcoholysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 483
15.5.3 Flame Retardant Master Batch . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 483
15.5.4 Graphene Nanoplatelets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 483
15.5.5 Shape-Memory Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 483
Contents xvii
15.5.6 Medical Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 484

References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 484
16. Compatibilization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 497

16.1 Equipment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 497
16.2 Basic Terms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 497
16.2.1 Thermodynamic Compatibility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 497
16.2.2 Thermodynamic Models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 498
16.2.3 Particle Size . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 498
16.2.4 Interfacial Slip . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 498
16.2.5 Interpolymer Radical Coupling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 498
16.2.6 Technological Compatibility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 499
16.3 Interpenetrating Polymer Networks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 499
16.4 Compatibilization by Additives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 499
16.4.1 Poly(ethylene) Blended with Inorganic Fillers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 500
16.4.2 Filler Materials without Chemical Compatibilizers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 500
16.4.3 Modified Inorganic Fillers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 502
16.4.4 Clay Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 502
16.4.5 Graphene Oxide Sheets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 502
16.4.6 Poly(propylene) Poly(acrylonitrile-butadiene-styrene) Blends . . . . . . . . . . . . . . . . . . . . . . . . . . 502
16.4.7 Poly(propylene)-Grafted Thermally Reduced Graphene Oxide . . . . . . . . . . . . . . . . . . . . . . . . . . 503
16.4.8 Thermoplastic Elastomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 503
16.4.9 Polyamide 6,6 and Poly(butylene terephthalate) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 504
16.4.10 Poly(ethylene)/Wood Flour Composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 504
16.4.11 Recycled Polyolefins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 504
16.4.12 Block Copolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 504
16.4.13 Poly(ethylene terephthalate) and High-Density Poly(ethylene) . . . . . . . . . . . . . . . . . . . . . . . . . . 505
16.4.14 Poly(ethylene terephthalate) and High-Density Poly(propylene) . . . . . . . . . . . . . . . . . . . . . . . . 505
16.4.15 Impact Modification of Waste PET . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 506
16.4.16 Poly(ethylene terephthalate) and Poly(methyl methacrylate) . . . . . . . . . . . . . . . . . . . . . . . . . . . 506
16.4.17 Starch . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 506
16.4.18 Blends of Cellulose and Chitosan . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 507
16.4.19 Polysaccharide Reinforced Polymer Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 507
16.4.20 Biofiber Reinforced Poly(hydroxybutyrate-co-hydroxyvalerate) . . . . . . . . . . . . . . . . . . . . . . . . . 507
16.5 Reactive Compatibilization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 508
16.5.1 In situ Generation of Compatibilizer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 509
16.5.2 Coupling Agents for Compatibilization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 510
16.5.3 High-Molecular-Weight Peroxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 510
16.5.4 Vector Fluids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 511
16.5.5 Poly(ethylene) and Polyamide 6 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 511
16.5.6 Polyolefins and Poly(butylene terephthalate) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 512
16.5.7 Poly(lactic acid) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 513
16.5.8 Poly(l-lactide) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 517
16.5.9 Poly(ethylene-octene) and Polyamide 6 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 518
16.5.10 Ethylene Acrylic Acid Polymers and Polyamide 6 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 518
16.5.11 PPO and Polyamide 6 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 518
16.5.12 Poly(vinylidene fluoride) and Polyamide 6 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 519
16.5.13 Wheat Straw . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 519
16.5.14 Poly(butylene succinate) Spirulina Microalgae Composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . 519
16.5.15 Lignin and Switchgrass Poly(butylene succinate) Composites . . . . . . . . . . . . . . . . . . . . . . . . . . 519
16.5.16 Sisal Fibers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 519
16.5.17 Thermotropic Liquid Crystalline Polyesters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 520
16.5.18 Ionomers and Ionomeric Compatibilizers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 520
xviii Contents
16.5.19 Solid Polymer Electrolytes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 521

16.5.20 Poly(vinyl chloride) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 521
16.5.21 Poly(styrene) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 522
16.5.22 Polyolefins/Poly(ethylene oxide) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 525
16.5.23 Poly(phenylene sulfide) and Liquid Crystalline Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 525
16.5.24 LDPE/Thermoplastic Starch . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 526
16.5.25 PE and EVA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 526
16.5.26 SBR and EVA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 526
16.5.27 NBR and EPDM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 526
16.5.28 NBR and PA6 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 527
16.5.29 Poly(carbonate) and Poly(vinylidene fluoride) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 527
16.5.30 Poly(ethylene terephthalate) ABS Blends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 527
16.5.31 Bisphenol A-poly(carbonate) and ABS Copolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 528
16.5.32 Kevlar™ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 528
16.5.33 Polyamides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 528
16.5.34 Polyethers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 528
16.5.35 Polyolefins and Poly(ethylene terephthalate) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 529
16.5.36 Poly(urethane) and Poly(ethylene terephthalate) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 529
16.6 Starch Polyester Blends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 530
16.7 Functionalization of End Groups . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 530
16.7.1 Mechanisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 530
16.7.2 Amino-Terminated Nitrile Rubber . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 531
16.7.3 Functionalization of Olefinic End Groups of Poly(propylene) . . . . . . . . . . . . . . . . . . . . . . . . . . 531
16.7.4 Muconic Acid Grafted Polyolefin Compatibilizers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 533
16.7.5 Polyfunctional Polymers and Modified Polyolefin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 534
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 534
17. Rheology Control . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 547

17.1 Melt Flow Rate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 547
17.2 Rheology Control Techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 547
17.2.1 Structure-Property Relationships . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 548
17.2.2 Pelletizing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 548
17.3 Peroxides for Rheology Control . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 548
17.3.1 Hydroperoxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 549
17.3.2 Peroxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 549
17.3.3 Diacyl Peroxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 549
17.3.4 Ketone Peroxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 550
17.3.5 Masterbatches of Peroxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 551
17.3.6 Peresters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 551
17.3.7 Properties of Peroxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 552
17.3.8 Azo Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 553
17.4 Scavengers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 554
17.4.1 Stable Nitroxyl Radicals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 554
17.5 Mechanism of Degradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 554
17.5.1 Radiation Induced Degradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 555
17.6 High Melt Flow Poly(propylene) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 556
17.7 Irregular Flow Improvement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 556
17.8 Heterophasic Copolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 556
17.9 Poly(ethylene) from Waste Streams . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 557
17.10 Poly(propylene) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 558
17.10.1 Long-Chain Branched Poly(propylene) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 559
17.10.2 Effect of MFR on Temperature and Residence Time . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 559
17.10.3 Spruce Wood Particle Poly(propylene) Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 559
Contents xix
17.10.4 Low Emission Propylene Homopolymer With High Melt Flow . . . . . . . . . . . . . . . . . . . . . . . . . 560
17.11 Poly(styrene) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 560
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 560
18. Grafting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 563

18.1 The Techniques in Grafting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 563
18.1.1 Parameters that Influence Grafting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 563
18.1.2 Free-Radical Induced Grafting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 564
18.1.3 Polymer Brushes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 564
18.2 Polyolefins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 567
18.2.1 Monomers for Grafting onto Polyolefins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 567
18.2.2 Mechanism of Melt Grafting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 568
18.2.3 Side Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 568
18.2.4 Viscosity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 569
18.2.5 Ceiling Temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 569
18.2.6 Effect of Initiator Solubility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 569
18.2.7 Distribution of the Grafted Groups . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 570
18.2.8 Effect of Stabilizers on Grafting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 570
18.2.9 Radical Grafting of Polyolefins with Diethyl Maleate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 570
18.2.10 Inhibitors for the Homopolymerization of Maleic Anhydride . . . . . . . . . . . . . . . . . . . . . . . . . . . 571
18.2.11 Inhibitors for Crosslinking . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 571
18.2.12 Special Initiators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 571
18.2.13 Maleic Anhydride . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 573
18.2.14 Polyolefins Grafted with Itaconic Acid Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 574
18.2.15 Imidized Maleic Groups . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 575
18.2.16 Oxazoline-Modified Polyolefins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 575
18.2.17 Modification of Polyolefins with Vinylsilanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 575
18.2.18 Ethyl Diazoacetate-Modified Polyolefins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 575
18.2.19 Grafting Antioxidants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 576
18.2.20 Comonomer Assisted Free-Radical Grafting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 576
18.2.21 Radiation-Induced Grafting in Solution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 578
18.2.22 Characterization of Polyolefin Graft Copolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 578
18.2.23 PVC/LDPE Melt Blends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 578
18.3 Other Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 578
18.3.1 Poly(styrene) Functionalized with Maleic Anhydride . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 579
18.3.2 Multifunctional Monomers for PP/PS Blends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 579
18.3.3 Poly(methyl methacrylate) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 579
18.3.4 Poly(ethylene-co-methyl acrylate) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 579
18.3.5 n-Butyl Methacrylate Grafted onto Poly(vinyl chloride) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 580
18.3.6 Starch Esterification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 580
18.3.7 Starch Grafted Acrylics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 581
18.3.8 Cellulose . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 581
18.3.9 Thermoplastic Phenol/Formaldehyde Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 582
18.3.10 Polyesters and Poly(urethane)s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 582
18.3.11 Polyacrylic Hot-Melt Pressure-Sensitive Adhesive . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 583
18.4 Terminal Functionalization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 583
18.4.1 Ene Reaction with Poly(propylene) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 583
18.4.2 Styrene Butadiene Rubber . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 584
18.4.3 Diels–Alder Reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 584
18.5 Grafting onto Surfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 584
18.5.1 Grafting onto Poly(ethylene) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 584
18.5.2 Grafting onto Poly(vinylidene fluoride) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 588
18.5.3 Grafting onto Poly(tetrafluoroethylene) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 588
xx Contents
18.6 Special Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 589

18.6.1 Stimuli-Responsive Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 589
18.6.2 Photovoltaic Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 589
18.6.3 Fuel Cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 589
18.6.4 Electrolyte Membrane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 590
18.6.5 Ion-Imprinted Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 590
18.6.6 Medical Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 590
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 592
19. Acrylic Dental Fillers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 601

19.1History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 601
19.2Methods for Development . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 601
19.3Polymeric Composite Filling Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602
19.4Monomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602
19.4.1 Acrylics and Methacrylics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602
19.4.2 Cyclic Monomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 605
19.4.3 Epoxy Monomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 606
19.4.4 Highly Loaded Composite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 606
19.5 Radical Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 606
19.5.1 Chemical Curing Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 607
19.5.2 Photo Curing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 609
19.5.3 Curing Techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 611
19.5.4 Dual Initiator Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 611
19.6 Inhibitors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 612
19.7 Additives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 612
19.7.1 Fillers and Reinforcing Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 612
19.7.2 Pigments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 615
19.7.3 Photostabilizers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 615
19.7.4 Caries Inhibiting Agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 615
19.7.5 Coloring or Tint Agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 616
19.7.6 Adhesion Promoter . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 616
19.7.7 Thermochromic Dye . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 616
19.8 Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 617
19.8.1 Effect of Denture Cleansers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 617
19.8.2 Polishing and Surface Roughness . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 618
19.8.3 Impact Strength and Fracture Morphology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 618
19.8.4 Effect of Polymerization Cycles on Mechanical Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 619
19.8.5 Optical Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 619
19.8.6 Chemical Stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 620
19.8.7 Cytotoxicity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 620
19.9 Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 623
19.9.1 Filling Techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 623
19.9.2 Primer Emulsions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 623
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 623
20. Toners . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 629

20.1 Toner Components . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 629
20.2 Toner Resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 630
20.3 Manufacture of Toner Resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 631
20.3.1 Co-emulsification of Insoluble Compounds with Toner Resins . . . . . . . . . . . . . . . . . . . . . . . . . . 631
20.3.2 Suspension Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 631
20.3.3 Terephthalic Ester Resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 632
20.3.4 Unsaturated Polyester Resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 632
Contents xxi
20.3.5 Biobased Polyesters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 632

20.3.6 Urethane Modified Resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 633
20.3.7 Toner Resins with Low Fix Temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 633
20.3.8 Toners for Textile Printing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 634
20.4 Characterization of Toners . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 635
20.4.1 Consistency . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 635
20.4.2 Health Aspects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 636
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 636
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 639
Acronyms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 639
Chemicals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 648
General Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 676
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Preface
Preface to Third Edition needed to produce resin precursors and the synthe-
sis of polymers. However, chemical topics relevant
Here, in the third edition, the most important liter-
to the manufacturer part are elaborated here. These
ature which appeared after 2014 has been included.
range from the manufacture of glass-fiber-reinforced
So the text is now updated up to 2017.
articles such as boats made by the amateur and in a
J. K. F. small scale dockyard to what takes place when a den-
tist is filling teeth. Industrial processes for the plastics
batch fabrication are described, in addition to their
Preface to Second Edition
end uses.
The first edition of this text appeared in 2005. In the The text describes the basic principles of reac-
second edition, the literature which appeared after tive resins as well as the most recent developments.
this date has been included. So the text is now up- Paints, coatings, and adhesives that are constituted
dated up to 2012. from resins are not dealt with here, even when the
curing mechanisms are similar.
J. K. F. The past art is discussed by reference to mono-
graphs, whereas the recent developments are docu-
Preface to First Edition mented by references in the scientific literature and
Most of the synthetic polymers are produced in the patent literature after 2000. In some topics, e.g.,
chemical plants and delivered to a plastics manu- urea-formaldehyde resins, the present research activ-
facturer who does the formulating, blending, extrud- ity is low. In other areas, such as resins used for
ing, or molding in order to fabricate articles. The nanocomposites, there are many recent papers. Even
processes required for the final product are purely those resins, for which the research activity is rather
physical that occur essentially without any chemical dormant at the moment, find widespread use and well
reaction of the polymer. Since most of the polymers established applications. They are not covered here
are immiscible, there is not much room to modify because they are presented in general reviews cited at
the polymer properties during the plastics manufac- the beginning of the respective chapters. Newer ap-
turing. The properties of the final product are often plications of these resins are discussed in detail.
modified by the actions of additives. The text originates from a lecture manuscript de-
A minor number of polymers, usually called veloped by the author that has been expanded into
resins, are delivered as precursors by the chemical a monograph. The original literature presented here
industry to the manufacturer. Here, the manufacturer covers the period until July 2004. The text is at a
gets to the final article by a chemical reaction. There
level that a chemist with a general eduction in poly-
also exists an in-between state where polymers can
mer chemistry should understand. Further, the text is
be modified by reactive extrusion and grafting. The
addressed to the advanced student of plastics engi-
modification of polymers is advantageous if com-
paratively small changes of certain properties are neering and the practicing engineer.
needed that cannot be achieved in chemical plants.
Since many different precursors of the final resin can How to Use this Book
be combined, the variability of, and thus the ability
to, modify the final properties are much more pro- Utmost care has been taken to present reliable data.
nounced in comparison to the rest of polymers. Because of the vast variety of material presented here,
This is the topic with which the present book however, it cannot be complete in all relevant aspects,
deals, namely, chemical reactions that take place dur- and it is recommended that the reader study the orig-
ing the final stage of part fabrication from plastics. inal literature for complete information. Therefore,
The text does not deal with the chemical reactions the author cannot assume responsibility for the com-
xxiii
xxiv Reactive Polymers: Fundamentals and Applications
pleteness and validity of, nor for the consequences difficult. I apologize here for this somewhat unsatis-
of, the use of the material presented here. Every at- factory situation.
tempt was made to identify trademarked products in
this volume; however, there were some that the au- Acknowledgments
thor was unable to locate, and we apologize for any
inadvertent omission. The continuous interest and the promotion by Pro-
fessor Wolfgang Kern, the head of the department
is highly appreciated. I am indebted to our univer-
Index sity librarians, Dr. Christian Hasenhüttl, Dr. Johann
There are three indices: an index of acronyms, an in- Delanoy, Franz Jurek, Margit Keshmiri, Dolores Kn-
dex of chemicals, and a general index. Unfortunately abl, Friedrich Scheer, Christian Slamenik, and Renate
the acronyms presented in the literature are not al- Tschabuschnig for support in literature acquisition.
I also want to express my gratitude to all the scientists
ways consistent. This means that in a few cases the
who have carefully published their results concerning
same acronym stands for different terms.
the topics dealt with here. This book could not have
Further, in the literature the acronyms are some- been otherwise compiled.
times expanded in a different way, in particular for I would like to thank Dr. Sina Ebnesajjad, Editor
chemical names. The author has not unified the sys- of Plastics Design Library (PDL), for his review and
tem of chemical names, even when the same com- comments on the manuscript.
pound appears with different names, because other-
wise back tracing in the original literature would be J. K. F.
1 Unsaturated Polyester Resins
Unsaturated polyester resins consist of two polymers, 1.2.1 Monomers for an

i.e., a short-chain polyester containing polymerizable Unsaturated Polyester
double bonds and a vinyl monomer. The curing re-
action consists of a copolymerization of the vinyl Monomers used for unsaturated polyesters are shown
monomer with the double bonds of the polyester. In in Table 1.1 and in Figures 1.1 and 1.2. Unsaturated
the course of curing, a three-dimensional network diols are only rarely used.
is formed. Unsaturated polyester resins belong to
the group of so-called thermosets. There are several
1.2.1.1 Alcohol Components
monographs and reviews on unsaturated polyesters The most common alcohol components are 1,2-
and unsaturated polyester resins [1–7]. propylene glycol and ethylene glycol (EG). Ether
We will differentiate between unsaturated poly- containing alcohols exhibit better air drying prop-
esters and unsaturated polyester resins. Unsaturated erties and are used in topcoats. Polyesters based on
polyesters are the polyesters as they emerge from the unsaturated diols can be prepared by the transester-
condensation vessel. They are rarely sold as such, ification of diethyl adipate with unsaturated diols,
because they are brittle at room temperature and e.g., cis-2-butene-1,4-diol, and 2-butyne-1,4-diol.
difficult to handle. Instead, whenever a polyester is The transesterification method is a suitable proce-
freshly synthesized in a plant, it is mixed with the dure for the preparation of unsaturated polyesters
vinyl monomer in the molten state. Thus materials in comparison to the direct polycondensation [14].
that are viscous at room temperature, with a styrene cis-2-Butene-1,4-diol, the most available aliphatic
unsaturated diol, has been used to produce some
content of ca. 60% are sold. Such a mixture of an un-
valuable polymers such as graftable unsaturated seg-
saturated polyester with the vinyl polymer is referred
mented poly(urethane)s and crosslinkable polyesters
to here as an unsaturated polyester resin.
for medical purposes.
Chemically modified soybean oil is an inexpen-
1.1 History sive alternative candidate for unsaturated polyester
(UP) compositions. In addition, when reinforced with
It was realized long ago that some natural oils as well
natural fibers, these composites could yield compa-
as alkyd resins can be dried by certain additives and
rable and adequate properties to common products.
used as coatings. This drying results from a poly- Acrylated epoxidized soybean oil or maleated acry-
merization of the unsaturated moieties in the ester lated epoxidized soybean oil can be used for the syn-
molecules. Next it was discovered that the addition thesis of a prepolymer that contains vinyl groups.
of styrene would accelerate the drying. The invention These groups are then copolymerized with styrene,
of unsaturated polyester resins is ascribed to Carleton as common [15].
Ellis (1876–1941). The first patents with regard to Isosorbide is referred to as a sugar diol because it
polyester resins emerged in the 1930s [8–10]. Com- is derived from D-glucose which ultimately is gen-
mercial production started in 1941 already reinforced erated from starch [16]. Isosorbide can be included
with glass fibers for radar domes, also referred to as as a glycol into unsaturated polyesters using standard
radomes. polyester synthetic techniques.
Formulations that are using an isosorbide-modi-
1.2 Monomers fied unsaturated polyester together with maleic acid,
fumaric acid, itaconic acid, or maleic anhydride have
According to the composition of an unsaturated been developed. These formulations exhibit a bet-
polyester resin, the monomers can be grouped into ter shrink control in molding compound formula-
two main classes, i.e., components for the polyester tions with standard low profile additives than their
and components for the vinyl monomer. non-isosorbide-modified analogs. Such resin compo-
Reactive Polymers: Fundamentals and Applications. http://dx.doi.org/10.1016/B978-0-12-814509-8.00001-4

Copyright © 2018 Elsevier Inc. All rights reserved. 1
2 Reactive Polymers: Fundamentals and Applications
Table 1.1 Monomers for Unsaturated Polyesters
Saturated alcohols Remarks

1,2-Propylene glycol Most common glycol
Ethylene glycol Less compatible with styrene than Propylene glycol
Diethylene glycol Good drying properties
Neopentyl glycol Good hydrolysis resistance
Glycerol Trifunctional alcohol, for branched polyesters. Danger of crosslinking
during condensation
Tetrabromobisphenol A (TBBPA) Flame retardant
Trimethylol propane Trifunctional alcohol, cheaper than glycerol
Trimethylol propane mono allyl ether Weather resistant for coatings [11,12]
Undecanol Used as chain stopper
Saturated acids and anhydrides Remarks
Phthalic anhydride Most common anhydride
Isophthalic acid Good hydrolysis resistance
Terephthalic acid Superior hydrolysis resistance
HET acid Flame retardant systems. In fact, even when addressed as HET acid,
the HET anhydride is used
Tetrabromophthalic anhydride Flame retardant systems
Adipic acid Soft resins
Sebacic acid Soft resins
o-Carboxy phthalanilic acid [13]
Unsaturated acids and anhydrides Remarks
Maleic anhydride Most common
Fumaric acid Copolymerizes better with styrene than maleic anhydride
Itaconic acid
pounds and may be components of fiber reinforced

composites or other composite materials [16].
It has been found that the use of isosorbide in
combination with maleic anhydride results in a strong
increase of the viscosity of the diluted resin [17].
To get a resin composition with a relatively low
viscosity, while the thermal stability of the cured ob-
jects is maintained or even increased, it has been
discovered that an isosorbide containing resin and
C5 −C10 unsaturated diacid building block is helpful.
Preferably, itaconic acid or anhydride can be used for
the C5 −C10 unsaturated diacid building blocks. This
is especially advantageous as itaconic acid or its an-
hydride can be derived from a non-fossil source, such
as corn [17,18].
1.2.1.2 Acid and Anhydride Components

Figure 1.1 Diols and triols used for unsaturated A general purpose industrial unsaturated polyester is
polyester resins. made from 1,2-propylene glycol, phthalic anhydride,
and maleic anhydride. The most commonly used
vinyl monomer is styrene. Maleic anhydride with-
sitions may be applied in molding compounds like out phthalic anhydride would yield a polyester with
sheet molding compounds or bulk molding com- a high density of double bonds along the polyester
1: Unsaturated Polyester Resins 3
are more stable than those made from phthalic an-

hydride. That is why these polyesters with neopentyl
glycol are used in aggressive environments and also
as gel coats and topcoats. A gel coat is the first layer
of a multilayer material; the top coat is the layer on
the opposite side. For instance, if a polyester boat
is built, the gel coat is first painted into the model.
Then a series of glass fiber reinforced laminates are
applied, and finally the top coat is painted.
Isomerization. During the synthesis of the poly-

ester, maleic anhydride partly isomerizes to fumaric
acid. The isomerization follows a second-order kinet-
ics because of the catalysis by maleic acid. The acti-
vation energy of the isomerization is ca. 63.2 kJ/mol
[19].
2-Methyl-1,3-propanediol offers significant pro-
cess advantages to resin producers because it is an
easily handled liquid, it has a high boiling point,
and it has two primary hydroxyl groups for rapid
condensations. Polyester resins produced from 2-
methyl-1,3-propanediol using conventional conden-
sation polymerization, however, have relatively low
fumarate contents (60 to 70%), and simply increase
the reaction temperature to promote isomerization
causing color problems.
Figure 1.2 Acids and anhydrides used for unsatu- The two-step process helps increase the degree of
rated polyester resins. isomerization for such systems. First, the aromatic
dicarboxylic acid is allowed to react with 2-methyl-
chain. This would result in a high crosslinking den- 1,3-propanediol at a temperature of up to 225 °C to
sity of the cured product, thus in a brittle product. produce an ester diol intermediate. In the second step,
Therefore, the unsaturated acid component is always the intermediate reacts with maleic anhydride and
diluted with an acid with non-polymerizable double with 1,2-propylene glycol. The resulting unsaturated
bonds. Note that aromatic double bonds also will polyester resin has a fumarate content greater than
not polymerize with vinyl components. The double about 85% [20]. The high fumarate content helps
bond in HET acid will not polymerize. Fumaric acid the resins to cure quickly and thoroughly with vinyl
copolymerizes well with styrene, but fumaric acid is monomers, giving the resulting thermosets excellent
more costly than maleic anhydride. Therefore, maleic water resistance.
anhydride is the preferred unsaturated acid compo-
nent. Another aspect is that during the condensation 1.2.1.3 Amine Modifiers
of fumaric acid, 2 mol of water must be removed from The adducts of ethylene oxide (EO) or propylene ox-
the reaction mixtures, whereas in the case of maleic ide with N,N -diphenylethane-1,2-diamine or N,N-
anhydride only 1 mol of water must be removed. An- dimethyl-p-phenylene diamine and EO with N,N -
hydrides are preferred over the corresponding acids diphenylhexane-1,6-diamine can be used as modi-
because of the higher reactivity. fiers. When used in amounts up to 2%, the amines
Isophthalic acid and terephthalic acid cannot form substantially reduce the gelation time of these modi-
an anhydride. These compounds do not condense as fied unsaturated polyesters. However, as the reactiv-
fast as phthalic anhydride. On the other hand, the ity of the resins increases, their stability decreases
polyesters from isophthalic acid and terephthalic acid [21,22].
4 Reactive Polymers: Fundamentals and Applications
Table 1.2 Vinyl Monomers for Unsaturated Polyester

Resins
Monomer Remarks
Styrene Most common, but carcinogenic
p-Vinyl toluene Not really a substitute for styrene
α-Methylstyrene Slows the curing
Figure 1.3 Ene reaction between maleic acid and di- Methyl acrylate
cyclopentadiene. Methyl methacrylate Good optical properties
Diallyl phthalate
Triallyl cyanurate
Dicyclopentadiene-modified unsaturated polyes-

ters yield molded articles with excellent performance.
The function of dicyclopentadiene is to impart air
drying characteristics, low-profile properties, high
heat distortion, excellent weathering performance,
and increased filler dispersibility in the resulting
polymer [26].
Figure 1.4 Retro Diels–Alder reaction of dicyclopen- 1.2.2 Vinyl Monomers

tadiene and Diels–Alder reaction between maleic
acid units and cyclopentadiene. The vinyl monomer serves as solvent for the polyester
and reduces its viscosity. Further, it is the agent
of copolymerization in the course of curing. Vinyl
1.2.1.4 Dicyclopentadiene monomers for unsaturated polyester resins are shown
Dicyclopentadiene is used in a wide variety of appli- in Table 1.2 and in Figure 1.5.
cations, including elastomers, flame retardants, pes-
ticides, and resins for adhesives, coatings and rubber 1.2.2.1 Styrenes
tackifiers. Approximately 30% of the production is Styrene is the most widely used vinyl monomer for
used for unsaturated polyester resins because of its unsaturated polyesters. However, styrene has a car-
valuable properties [23].
cinogenic potential: therefore, replacing styrene by
Dicyclopentadiene polyester resins are synthe-
some other vinyl monomer has been discussed for
sized from dicyclopentadiene, maleic anhydride, and
years.
a glycol. The reaction is performed in the presence
With larger amounts of styrene the rigidity of the
of water to generate maleic acid from the maleic an-
material can be increased. α-Methylstyrene forms
hydride to form dicyclopentadiene maleate. The ene
less reactive radicals, and thus slows down the cur-
reaction is shown in Figure 1.3.
ing reaction. Therefore, α-methylstyrene is suitable
The maleate is esterified with the glycol to form
for decreasing the peak temperature during curing.
the unsaturated polyester resin [24,25]. The ene
Polar vinyl monomers, such as vinylpyridine, im-
adduct serves to form end-capped polyesters. At
prove the adhesion of the polyester to glass fibers,
higher temperatures dicyclopentadiene undergoes a
which is useful in preventing delamination.
retro Diels–Alder reaction and can add to the unsat-
urations of fumaric acid and maleic acid (as pointed
out in Figure 1.4), to form nadic acid units. When the
1.2.2.2 Acrylates and Methacrylates
dicyclopentadiene-modified unsaturated polyester is Acrylates improve outdoor stability. Methyl metha-
used for a molding material, the polyester is usually crylate, in particular, enhances the optical proper-
mixed with a radically polymerizable monomer and a ties. The refractive index can be varied with mixtures
polymerization initiator. This allows the viscosity or of styrene and methyl methacrylate close to that of
curing time of the molding material to be suitable for glass, so that fairly transparent materials could be
the molding operation. produced.
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usually there is a long slender beak; the legs are elongate, frequently
hairy; the tarsi bear long pulvilli and a small empodium. The
Empidae are an extensive family of flies, with predaceous habits, the
rostrum being used by the female as an instrument for impaling and
sucking other flies. They are occasionally very numerous in
individuals, especially in wooded districts. There is great variety;
there are nearly 200 species in Britain. The forms placed in the sub-
family Hybotinae are curious slender little Insects, with very convex
thorax and large hind legs. In Hemerodromia the front legs are
raptorial, the femora being armed with spines on which the tibiae
close so as to form a sort of trap. Many Empidae execute aërial
dances, and some of the species of the genus Hilara are notorious
for carrying veils or nets in the form of silken webs more or less
densely woven. This subject is comparatively new, the fact having
been discovered by Baron Osten Sacken in 1877,[414] and it is not at
all clear what purpose these peculiar constructions serve; it appears
probable that they are carried by means of the hind legs, and only by
the males. Mik thinks that in H. sartor the veil acts as a sort of
parachute, and is of use in carrying on the aërial performance, or
enhancing its effect; while in the case of other species, H. maura and
H. interstincta, the object appears to be the capture or retention of
prey, after the manner of spiders. The source of the silk is not
known, and in fact all the details are insufficiently ascertained. The
larvae of Empidae are described as cylindrical maggots, with very
small head, and imperfect ventral feet; the stigmata are
amphipneustic, the thoracic pair being, however, excessively small;
beneath the posterior pair there is nearly always a tooth- or spine-
like prominence present.
Fig. 235—A, Larva, B, pupa of Medeterus ambiguus. France. (After
Perris.)
Fam. 27. Dolichopidae.—Graceful flies of metallic colours, of

moderate or small size, and long legs; usually with bristles on the
thorax and legs, the halteres exposed, squamae being quite absent;
antennae of two short stout joints (of which the second is really two,
its division being more or less distinct), with a thread-like or hair-like
appendage. Proboscis short, fleshy. Claws, pulvilli, and empodium
small; wings with a simple system of nervures, those on the posterior
part of the wing are but few, there is no anterior basal cross-vein
between the discal and second basal cells, which therefore form but
one cell. This is also a very extensive family of flies, of which we
have probably about 200 species in Britain. They are conspicuous
on account of their golden, or golden-green colours, only a few being
yellow or black. The males are remarkable for the curious special
characters they possess on the feet, antennae, face, or wings.
These characters are not alike in any two species; they are believed
to be of the nature of ornaments, and according to Professor Aldrich
and others are used as such in courtship.[415] This family of flies
approaches very closely to some of the Acalyptrate Muscidae in its
characters. It is united by Brauer with Empidae to form the tribe
Orthogenya. Although the species are so numerous and abundant in
Europe, little is known as to their metamorphoses. Some of the
larvae frequent trees, living under the bark or in the overflowing sap,
and are believed to be carnivorous; they are amphipneustic; a
cocoon is formed, and the pupa is remarkable on account of the
existence of two long horns, bearing the spiracles, on the back of the
thorax; the seven pairs of abdominal spiracles being excessively
minute.[416]
Fig. 236—Wing of Trineura aterrima, one of the Phoridae. Britain.
Series 3. Cyclorrhapha Aschiza
Fam. 28. Phoridae.—Small flies, with very convex thorax, small

head, very small two-jointed antennae, bearing a long seta; femora
more or less broad; wings with two dark, thick, approximate veins,
meeting on the front margin near its middle, and besides these, three
or four very fine veins, that run to the margins in a sub-parallel
manner without forming any cells or forks. This obscure family of
flies is of small extent, but its members are extremely common in
Europe and North America, where they often occur in numbers
running on the windows of houses. It is one of the most isolated
groups of Diptera, and great difference of opinion prevails as to its
classification. The wing-nervuration is peculiar (but varies somewhat
in the species), the total absence of any cross-veins even on the
basal part of the wing being remarkable. There are bristles on the
head and thorax, but they are not arranged in a regular manner. The
larvae live in a great variety of animal and vegetable decaying
matter, and attack living Insects, and even snails, though probably
only when these are in a sickly or diseased condition. The
metamorphoses of several species have been described.[417] The
larvae are rather slender, but sub-conical in form, with eleven
segments and a very small head, amphipneustic, the body behind
terminated by some pointed processes. The pupa is remarkable; it is
contained in a case formed by the contracted and hardened skin of
the larva; though it differs much in form from the larva the
segmentation is distinct, and from the fourth segment there project
two slender processes. These are breathing organs, attached to the
prothorax of the imprisoned pupa; in what manner they effect a
passage through the hardened larval skin is by no means clear.
Perris supposes that holes for them pre-exist in the larval skin, and
that the newly-formed pupa by restless movements succeeds in
bringing the processes into such a position that they can pass
through the holes. The dehiscence of the puparium seems to occur
in a somewhat irregular manner, as in Microdon; it is never
Cyclorrhaphous, and according to Perris is occasionally
Orthorrhaphous; probably there is no ptilinum.
Fig. 237—Aenigmatias blattoides. × 27. Denmark. (After Meinert.)
The Insect recently described by Meinert as Aenigmatias blattoides,

[418] is so anomalous, and so little is known about it, that it cannot at
present be classified. It is completely apterous; the arrangement of
the body-segments is unlike that of Diptera, but the antennae and
mouth-parts are said to be like those of Phoridae. The Insect was
found near Copenhagen under a stone in the runs of Formica fusca.
Meinert thinks it possible that the discovery of the male may prove
Aenigmatias to be really allied to Phoridae, and Mik suggests that it
may be the same as Platyphora lubbocki, Verrall, known to be
parasitic on ants. Dahl recently described a wingless Dipteron, found
living as a parasite on land-snails in the Bismarck archipelago, under
the name of Puliciphora lucifera, and Wandolleck has recently made
for this and some allies the new family Stethopathidae. It seems
doubtful whether these forms are more than wingless Phoridae.
Fam. 29. Platypezidae.—Small flies, with porrect three-jointed

antennae, first two joints short, third longer, with a terminal seta; no
bristles on the back; hind legs of male, or of both sexes, with
peculiar, broad, flat tarsi; the middle tibiae bear spurs; there is no
empodium. Platypezidae is a small family of flies, the classification of
which has always been a matter of considerable difficulty, and is still
uncertain. The larvae are broad and flat, fringed at the margin with
twenty-six spines; they live between the lamellae of Agaric fungi. At
pupation the form alters but little; the imago emerges by a horizontal
cleft occurring at the margins of segments two and four.[419] We
have four genera (Opetia, Platycnema, Platypeza, Callomyia), and
nearly a score of species of Platypezidae in our British list, but very
little seems to be known about them. There is much difference in the
eyes of the sexes, in some at any rate of the species, they being
large and contiguous in the male, but widely separated in the female.
Fig. 238—Head of Pipunculus sp. A, Seen from in front; B, side view,

showing an antenna magnified. Pyrenees.
Fam. 30. Pipunculidae.[420]—Small flies, with very short antennae

bearing a long seta that is not terminal; head almost globular,
formed, except at the back, almost entirely by the large conjoined
eyes; the head is only slightly smaller in the female, but in the male
the eyes are more approximate at the top. This is another of the
small families of flies, that seems distinct from any other, though
possessing no very important characters. In many of the flies that
have very large eyes, the head is either flattened (i.e. compressed
from before backwards, as in Tabanidae, Asilidae), or forced beneath
the humped thorax (as in Acroceridae), but neither of these
conditions exists in Pipunculus; in them the head extends far
forwards, so that the area of the eye compared with the size of the
body is perhaps greater than in any other Diptera. The general form
is somewhat that of Anthrax, but the venation on the hind part of the
wing is much less complex. There is a remarkable difference
between the facets on the front and the back of these great eyes.
We have three genera and about a dozen species of Pipunculidae in
Britain but apparently they are far from common Insects. What is
known about the life-history is almost confined to an imperfect
observation by Boheman, who found the larva of P. fuscipes living
after the manner of a Hymenopterous parasite in the body of a small
Homopterous Insect.[421] The pupa seems to be of the type of that of
Syrphidae.
Fam. 31. Conopidae.—Elegant flies of moderate size, of varied
colours, with abdomen slender at the base, at the tip strongly
incurved and thicker; antennae inserted close together on a
prominence, three-jointed, first joint sometimes very short. The upper
surface of the body without bristles or with but few. There is a
slender, elongate proboscis, which is retractile and usually invisible.
This rather small family of flies includes some of the most
remarkable forms of Diptera; it includes two divisions, the Conopinae
with long antennae terminated by a very minute pointed process,
and Myopinae with shorter antennae bearing a hair that is not placed
at the end of the third joint. The former are the more wasp-like and
elegant; the Myopinae being much more like ordinary flies, though
they frequently have curious, inflated heads, with a white face. The
mode of life of the larva of Conops is peculiar, it being parasitic in the
interior of Bombus, or other Hymenoptera. They have been found to
attack Bombus, Chalicodoma, Osmia, Vespa, Pompilus, and other
Aculeates. Williston says that Orthoptera are also attacked. Conops
has been seen to follow Bumble-bees and alight on them, and
Williston says this act is accompanied by oviposition, the larva that is
hatched boring its way into the body of the bee. Others have
supposed that the flies enter the bees' nests and place their eggs in
the larvae or pupae; but this is uncertain, for Conops has never been
reared from a bee-larva or pupa, though it has frequently been
procured from the imago: cases indeed having been recorded in
which Conops has emerged from the body of a Bombus several
months after the latter had been killed and placed in an
entomologist's collection. The larva is broad, and when full grown
apparently occupies nearly all the space of the interior of the
abdomen of the bee; it has very peculiar terminal stigmata. The pupa
is formed in the larval skin, which is greatly shortened and indurated
for the purpose; this instar bears, in addition to the posterior
stigmata, a pair of slightly projecting, anterior stigmata. We have
several species of Conopidae in Britain; those belonging to the
division Conopinae are all rare Insects, but the Myopinae are not so
scarce; these latter are believed to be of similar habits with the
Conopinae, though remarkably little is known about them. This is
another of the numerous families, the relations of which are still a
subject for elucidation. Brauer places the Conopidae in his section
Schizophora away from Syrphidae, but we do not comprehend on
what grounds; an inspection of the head shows that there is no
frontal lunule as there is in Eumyiidae; both Myopa and Conops
agreeing fairly well with Syrphus as to this. We therefore place the
family in its old position near Syrphus till the relations with
Acalypterate Muscidae shall be better established.
Fam. 32. Syrphidae (Hover-flies).—Of moderate or rather large

size, frequently spotted or banded with yellow, with a thick fleshy
proboscis capable of being withdrawn into a cleft on the under side
of the head; antennae not placed in definite cavities, three-jointed
(usually very short), and leaving a seta that is not terminal in
position, and may be feathered. Squama variable, never entirely
covering the halteres; the chief (third to fifth) longitudinal veins of the
wings connected near their termination by cross-veins and usually
thus forming a sort of short margin parallel with the hind edge of the
wing; a more or less imperfect false nervure running between the
third and fourth longitudinal nervures; no empodium and generally no
distinct system of bristles on the back of the body. The Syrphidae
(Fig. 212) form one of the largest and best known of all the families
of flies; they abound in our gardens where, in sunny weather, some
species may be nearly always seen hovering over flowers, or
beneath trees in places where the rays of the sun penetrate amidst
the shade. There are two or three thousand species known, so that
of course much variety exists; some are densely covered with hair
(certain Volucella and others), many are of elegant form, and some
bear a considerable resemblance to Hymenoptera of various groups.
The peculiar veining of the wings permits of their easy identification,
the line of two nervules, approximately parallel with the margin of the
distal part of the wing (Fig. 212, D), and followed by a deep bay,
being eminently characteristic, though there are some exceptions;
there are a few forms in which the antennae are exceptional in
having a terminal pointed process. The proboscis, besides the
membranous and fleshy lips, consists of a series of pointed slender
lancets, the use of which it is difficult to comprehend, as the Insects
are not known to pierce either animals or vegetables, their food
being chiefly pollen; honey is also doubtless taken by some species,
but the lancet-like organs appear equally ill-adapted for dealing with
it. The larvae are singularly diversified; first, there are the eaters of
Aphidae, or green-fly; some of these may be generally found on our
rose-bushes or on thistles, when they are much covered with Aphids;
they are soft, maggot-like creatures with a great capacity for
changing their shape and with much power of movement, especially
of the anterior part of the body, which is stretched out and moved
about to obtain and spear their prey: some of them are very
transparent, so that the movements of the internal organs and their
vivid colours can readily be seen: like so many other carnivorous
Insects, their voracity appears to be insatiable. The larvae of many of
the ordinary Hover-flies are of this kind. Eristalis and its allies are
totally different, they live in water saturated with filth, or with
decaying vegetable matter (the writer has found many hundreds of
the larvae of Myiatropa florea in a pool of water standing in a hollow
beech-tree). These rat-tailed maggots are of great interest, but as
they have been described in almost every work on entomology, and
as Professor Miall[422] has recently given an excellent account of
their peculiarities, we need not now discuss them. Some of the flies
of the genus Eristalis are very like honey-bees, and appear in old
times to have been confounded with them; indeed, Osten Sacken
thinks this resemblance gave rise to the "Bugonia myth," a fable of
very ancient origin to the effect that Honey-bees could be procured
from filth, or even putrefying carcases, by the aid of certain
proceedings that savoured slightly of witchcraft, and may therefore
have increased the belief of the operator in the possibility of a
favourable result. It was certainly not bees that were produced from
the carcases, but Osten Sacken suggests that Eristalis-flies may
have been bred therein.
In the genus Volucella we meet with a third kind of Syrphid larva.

These larvae are pallid, broad and fleshy, surrounded by numerous
angular, somewhat spinose, outgrowths of the body; and have
behind a pair of combined stigmata, in the neighbourhood of which
the outgrowths are somewhat larger; these larvae live in the nests of
Bees and Wasps, in which they are abundant. Some of the
Volucella, like many other Syrphidae, bear a considerable
resemblance to Bees or Wasps, and this has given rise to a modern
fable about them that appears to have no more legitimate basis of
fact than the ancient Bees-born-of-carcases myth. It was formerly
assumed that the Volucella-larvae lived on the larvae of the Bees,
and that the parent flies were providentially endowed with a bee-like
appearance that they might obtain entrance into the Bees' nests
without being detected, and then carry out their nefarious intention of
laying eggs that would hatch into larvae and subsequently destroy
the larvae of the Bees. Some hard-hearted critic remarked that it was
easy to understand that providence should display so great a
solicitude for the welfare of the Volucella, but that it was difficult to
comprehend how it could be, at the same time, so totally indifferent
to the welfare of the Bees. More recently the tale has been revived
and cited as an instance of the value of deceptive resemblance
resulting from the action of natural selection, without reference to
providence. There are, however, no facts to support any theory on
the subject. Very little indeed is actually known as to the habits of
Volucella in either the larval or imaginal instars; but the little that is
known tends to the view that the presence of the Volucella in the
nests is advantageous to both Fly and Bee. Nicolas has seen
Volucella zonaria enter the nest of a Wasp; it settled at a little
distance and walked in without any fuss being made. Erné has
watched the Volucella-larvae in the nests, and he thinks that they eat
the waste or dejections of the larvae. The writer kept under
observation Volucella-larvae and portions of the cells of Bombus,
containing some larvae and pupae of the Bees and some honey, but
the fly-larvae did not during some weeks touch any of the Bees or
honey, and ultimately died, presumably of starvation. Subsequently,
he experimented with Volucella-larvae and a portion of the comb of
wasps containing pupae, and again found that the flies did not attack
the Hymenoptera; but on breaking a pupa of the Wasp in two, the fly-
larvae attacked it immediately and eagerly; so that the evidence
goes to show that the Volucella-larvae act as scavengers in the
nests of the Hymenoptera. Künckel d'Herculais has published an
elaborate work on the European Volucella; it is remarkable for the
beauty of the plates illustrating the structure, anatomy and
development, but throws little direct light on the natural history of the
Insects. V. bombylans, one of the most abundant of our British
species, appears in two forms, each of which has a considerable
resemblance to a Bombus, and it has been supposed that each of
the two forms is specially connected with the Bee it resembles, but
there is no evidence to support this idea; indeed, there is some little
evidence to the contrary. The genus Merodon has larvae somewhat
similar to those of Volucella, but they live in bulbs of Narcissus; M.
equestris has been the cause of much loss to the growers of Dutch
bulbs; this Fly is interesting on account of its great variation in colour;
it has been described as a whole series of distinct species.
The most remarkable of the numerous forms of Syrphid larvae are

those of the genus Microdon (Fig. 239), which live in ants' nests.
They have no resemblance to Insect-larvae, and when first
discovered were not only supposed to be little Molluscs, but were
actually described as such under the generic names of Parmula and
Scutelligera. There is no appearance of segmentation of the body;
the upper surface is covered by a sort of network formed by curved
setae, which help to retain a coating of dirt; there is no trace
externally of any head, but on the under surface there is a minute
fold in which such mouth-organs as may be present are probably
concealed; the sides of the body project so as to form a complex
fringing arrangement; the terminal stigmata are very distinct, the
lateral processes connected with them (the "Knospen" of Dr.
Meijere), are, however, very irregular and placed at some distance
from the stigmatic scar. Pupation occurs by the induration of the
external covering and the growth from it, or rather through it, of two
short horns in front. Inside this skin there is formed a soft pupa, of
the kind usual in Cyclorrhaphous flies; the dehiscence of the external
covering is, however, of unusual nature, three little pieces being
separated from the anterior part of the upper surface, while the lower
face remains intact. The account of the pupation given by Elditt[423]
is not complete: the two horns that project are, it would appear, not
portions of the larval skin, but belong to the head of the pupa, and
according to Elditt are used to effect the dehiscence of the case for
the escape of the fly; there does not appear to be any head-vesicle.
Nothing is known as to the details of the life of these anomalous
larvae. M. Poujade has described two species found in France in the
nests of the ant Lasius niger.[424] The larva we figure was found by
Colonel Yerbury in nests of an Atta in Portugal, and an almost
identical larva was recently found by Mr. Budgett in Paraguay. The
flies themselves are scarce, Microdon mutabilis (formerly called M.
apiformis) being one of the rarest of British flies. They have the
antennae longer than is usual in Syrphidae, and the cross-veins at
the outside of the wing are irregularly placed, so that the contour is
very irregular: the resemblance to bees is very marked, and in some
of the South American forms the hind legs are flattened and hairy
like those of bees. The oviposition of Microdon has been observed
by Verhoeff;[425] he noticed that the fly was frequently driven away
by the ants—in this case, Formica sanguinea—but returned
undiscouraged to its task.
Fig. 239—Larva of Microdon sp. Portugal. A, Dorsal view of the larva, ×

4; 1, the stigmatic structure; B, posterior view of stigmatic
structure; C, a portion of the marginal fringe of the body.
A brief résumé of the diverse modes of life of Syrphid larvae has

been given by Perris,[426] and he also gives some information as to
the curious horns of the pupae, but this latter point much wants
elucidation. Whether the Syrphidae, or some of them, possess a
ptilinum that helps them to emerge from the pupa is more than
doubtful, though its existence has been affirmed by several authors
of good repute.[427]
Fig. 240.—Diopsis apicalis. Natal. A, The fly; B, extremity of cephalic
protuberance, more magnified. a, The eye; b, the antenna; C,
middle of head, front view; c, ocelli.
Series 4. Cyclorrhapha Schizophora
Fam. 33. Muscidae acalyptratae.—This group of flies has been the

least studied of all the Diptera; it is generally treated as composed of
twenty or thirty different families distinguished by very slight
characters. It is, however, generally admitted by systematists that
these assemblages have not the value of the families of the other
divisions of Diptera, and some even go so far as to say that they are
altogether only equivalent to a single family. We do not therefore
think it necessary to define each one seriatim; we shall merely
mention their names, and allude to certain points of interest
connected with them. Taken collectively they may be defined as very
small flies, with three-jointed antennae (frequently looking as if only
two-jointed), bearing a bristle that is not terminally placed; frequently
either destitute of squamae or having these imperfectly developed so
as not to cover the halteres; and possessing a comparatively simple
system of nervuration, the chief nervures being nearly straight, so
that consequently few cells are formed. These characters will
distinguish the group from all the other Diptera except from forms of
Aschiza, and from certain Anthomyiidae, with both of which the
Acalyptratae are really intimately connected. Considerable difference
of opinion prevails as to the number of these divisions, but the
families usually recognised are:—
1. Doryceridae.
2. Tetanoceridae.
3. Sciomyzidae.
4. Diopsidae.
5. Celyphidae.
6. Sepsidae incl. Piophilidae.
7. Chloropidae (= Oscinidae).
8. Ulidiidae.
9. Platystomidae.
10. Ephydridae.
11. Helomyzidae.
12. Dryomyzidae.
13. Borboridae.
14. Phycodromidae.
15. Thyreophoridae.
16. Scatophagidae. (= Scatomyzidae).
17. Geomyzidae incl. Opomyzidae.
18. Drosophilidae; incl. Asteidae.
19. Psilidae.
20. Tanypezidae (= Micropezidae).
21. Trypetidae.
22. Sapromyzidae incl. Lonchaeidae.
23. Rhopalomeridae.
24. Ortalidae.
25. Agromyzidae incl. Phytomyzidae.
26. Milichiidae.
27. Octhiphilidae.
28. Heteroneuridae.
29. Cordyluridae.
Brauer associates Conopidae with Acalyptrate Muscids, and calls

the Group Holometopa; applying the term Schizometopa to the
Calyptrate Muscidae.
No generalisation can yet be made as to the larvae of these

divisions, neither can any characters be pointed out by which they
can be distinguished from the larvae of the following families. In their
habits they have nothing specially distinctive, and may be said to
resemble the Anthomyiidae, vegetable matter being more used as
food than animal; many of them mine in the leaves or stems of
plants; in the genus Dorycera the larva is aquatic, mining in the
leaves of water-plants, and in Ephydridae several kinds of aquatic
larvae are found, some of which are said to resemble the rat-tailed
larvae of Syrphidae; certain of these larvae occur in prodigious
quantities in lakes, and the Insects in some of their early stages
serve the Mexicans as food, the eggs being called Ahuatle, the
larvae Pusci, the pupae Koo-chah-bee. Some of the larvae of the
Sciomyzidae are also aquatic: that of Tetanocera ferruginea is said
by Dufour to consist only of eight segments, and to be metapneustic;
Brauer considers the Acalyptrate larvae to be, however, in general,
amphipneustic, like those of Calyptratae. The Chloropidae are a very
important family owing to their occasional excessive multiplication,
and to their living on cereals and other grasses, various parts of
which they attack, sometimes causing great losses to the
agriculturist. The species of the genus Chlorops are famous for the
curious habit of entering human habitations in great swarms:
frequently many millions being found in a single apartment.
Instances of this habit have been recorded both in France and
England, Cambridge being perhaps the place where the
phenomenon is most persistently exhibited. In the year 1831 an
enormous swarm of C. lineata was found in the Provost's Lodge at
King's College and was recorded by Leonard Jenyns; in 1870
another swarm occurred in the same house if not in the same room.
[428] Of late years such swarms have occurred in certain apartments
in the Museums (which are not far from King's College), and always
in the same apartments. No clue whatever can be obtained as to
their origin; and the manner in which these flies are guided to a small
area in numbers that must be seen to be believed, is most
mysterious. These swarms always occur in the autumn, and it has
been suggested that the individuals are seeking winter quarters.
Fig. 241—Celyphus (Paracelyphus) sp. West Africa. A, The fly seen
from above; a, scutellum; b, base of wing: B, profile, with tip of
abdomen bent downwards; a, scutellum; b, b, wing; c, part of
abdomen.
Several members of the Acalyptratae have small wings or are

wingless, as in some of our species of Borborus. The Diopsidae—
none of which are European—have the sides of the head produced
into long horns, at the extremity of which are placed the eyes and
antennae; these curiosities (Fig. 240) are apparently common in both
Hindostan and Africa. In the horned flies of the genus Elaphomyia,
parts of the head are prolonged into horns of very diverse forms
according to the species, but bearing on the whole a great
resemblance to miniature stag-horns. A genus (Giraffomyia) with a
long neck, and with partially segmented appendages, instead of
horns on the head, has been recently discovered by Dr. Arthur Willey
in New Britain. Equally remarkable are the species of Celyphus; they
do not look like flies at all, owing to the scutellum being inflated and
enlarged so as to cover all the posterior parts of the body as in the
Scutellerid Hemiptera: the wings are entirely concealed, and the
abdomen is reduced to a plate, with its orifice beneath, not terminal;
the surface of the body is highly polished and destitute of bristles.
Whether this is a mimetic form, occurring in association with similar-
looking Bugs is not known. The North American genus Toxotrypana
is furnished with a long ovipositor; and in this and in the shape of the
body resembles the parasitic Hymenoptera. This genus was placed
by Gerstaecker in Ortalidae, but is considered by later writers to be a
member of the Trypetidae. This latter family is of considerable
extent, and is remarkable amongst the Diptera for the way in which
the wings of many of its members are ornamented by an elaborate
system of spots or marks, varying according to the species.
Fam. 34. Anthomyiidae.—Flies similar in appearance to the House-

fly; the main vein posterior to the middle of the wing (4th longitudinal)
continued straight to the margin, not turned upwards. Eyes of the
male frequently large and contiguous, bristle of antenna either
feathery or bare. This very large family of flies is one of the most
difficult and unattractive of the Order. Many of its members come
close to the Acalyptrate Muscidae from which they are distinguished
by the fact that a well-developed squama covers the halteres; others
come quite as close to the Tachinidae, Muscidae and
Sarcophagidae, but may readily be separated by the simple, not
angulate, main vein of the wing. The larval habits are varied. Many
attack vegetables, produce disintegration in them, thus facilitating
decomposition. Anthomyia brassicae is renowned amongst market
gardeners on account of its destructive habits. A. cana, on the
contrary, is beneficial by destroying the migratory Locust
Schistocerca peregrina; and in North America, A. angustifrons
performs a similar office with Caloptenus spretus. One or two
species have been found living in birds; in one case on the head of a
species of Spermophila, in another case on a tumour of the wing of a
Woodpecker. Hylemyia strigosa, a dung-frequenting species, has the
peculiar habit of producing living larvae, one at a time; these larvae
are so large that it would be supposed they are full grown, but this is
not the case, they are really only in the first stage, an unusual
amount of growth being accomplished in this stadium. Spilogaster
angelicae, on the other hand, according to Portschinsky, lays a small
number of very large eggs, and the resulting larvae pass from the
first to the third stage of development, omitting the second stage that
is usual in Eumyiid Muscidae.[429]
Fig. 242—Ugimyia sericariae. A, The perfect fly, × 3⁄2; B, tracheal
chamber of a silkworm, with body of a larva of Ugimyia projecting;
a, front part of the maggot; b, stigmatic orifice of the maggot; c,
stigma of the silkworm. (After Sasaki.)
Fam. 35. Tachinidae.—First posterior cell of wing nearly or quite

closed. Squamae large, covering the halteres: antennal arista bare:
upper surface of body usually bristly. This is an enormous family of
flies, the larvae of which live parasitically in other living Insects,
Lepidopterous larvae being especially haunted. Many have been
reared from the Insects in which they live, but beyond this little is
known of the life-histories, and still less of the structure of the larvae
of the Tachinidae, although these Insects are of the very first
importance in the economy of Nature. The eggs are usually
deposited by the parent-flies near or on the head of the victim; Riley
supposed that the fly buzzes about the victim and deposits an egg
with rapidity, but a circumstantial account given by Weeks[430]
discloses a very different process: the fly he watched sat on a leaf
quietly facing a caterpillar of Datana engaged in feeding at a
distance of rather less than a quarter of an inch. "Seizing a moment
when the head of the larva was likely to remain stationary, the fly
stealthily and rapidly bent her abdomen downward and extended
from the last segment what proved to be an ovipositor. This passed
forward beneath her body and between the legs until it projected
beyond and nearly on a level with the head of the fly and came in
contact with the eye of the larva upon which an egg was deposited,"
making an addition to five already there. Ugimyia sericariae does
great harm in Japan by attacking the silkworm, and in the case of
this fly the eggs are believed to be introduced into the victim by
being laid on mulberry leaves and swallowed with the food; several
observers agree as to the eggs being laid on the leaves, but the fact
that they are swallowed by the silkworm is not so certain. Sasaki has
given an extremely interesting account of the development of this
larva.[431] According to him, the young larva, after hatching in the
alimentary canal, bores through it, and enters a nerve-ganglion,
feeding there for about a week, after which the necessity for air
becoming greater, as usual with larvae, the maggot leaves the
nervous system and enters the tracheal system, boring into a tube
near a stigmatic orifice of the silkworm, where it forms a chamber for
itself by biting portions of the tissues and fastening them together
with saliva. In this it completes its growth, feeding on the interior of
the silkworm with its anterior part, and breathing through the
stigmatic orifice of its host; after this it makes its exit and buries itself
deeply in the ground, where it pupates. The work of rupturing the
puparium by the use of the ptilinum is fully described by Sasaki, and
also the fact that the fly mounts to the surface of the earth by the aid
of this same peculiar air-bladder, which is alternately contracted and
distended. Five, or more, of the Ugimyia-maggots may be found in
one caterpillar, but only one of them reaches maturity, and emerges
from the body. The Tachinid flies appear to waste a large proportion
of their eggs by injudicious oviposition; but they make up for this by
the wide circle of their victims, for a single species has been known
to infest Insects of two or three different Orders.
Fig. 243—Diagrammatic section of silkworm to show the habits of

Ugimyia. a, Young larva; b, egg of Ugimyia in stomach of the
silkworm; c, larva in a nerve-ganglion; d, larva entering a
ganglion; e, larva embedded in tracheal chamber, as shown in
Fig. 242, B. (After Sasaki.)
The species of Miltogramma—of which there are many in Europe

and two in England—live at the expense of Fossorial Hymenoptera
by a curious sort of indirect parasitism. They are obscure little flies,
somewhat resembling the common House-fly, but they are adepts on
the wing and have the art of ovipositing with extreme rapidity; they
follow a Hymenopteron as it is carrying the prey to the nest for its
young. When the wasp alights on the ground at the entrance to the
nest, the Miltogramma swoops down and rapidly deposits one or
more eggs on the prey the wasp designs as food for its own young.
Afterwards the larvae of the fly eat up the food, and in consequence
of the greater rapidity of their growth, the young of the
Hymenopteron perishes. Some of them are said to deposit living
larvae, not eggs. Fabre has drawn a very interesting picture of the
relations that exist between a species of Miltogramma and a
Fossorial Wasp of the genus Bembex[432]. We may remind the
reader that this Hymenopteron has not the art of stinging its victims
so as to keep them alive, and that it accordingly feeds its young by
returning to the nest at proper intervals with a fresh supply of food,
instead of provisioning the nest once and for all and then closing it.
This Hymenopteron has a habit of catching the largest and most
active flies—especially Tabanidae—for the benefit of its young, and it
would therefore be supposed that it would be safe from the
parasitism of a small and feeble fly. On the contrary, the
Miltogramma adapts its tactics to the special case, and is in fact
aided in doing so by the wasp itself. As if knowing that the wasp will
return to the carefully-closed nest, the Miltogramma waits near it,
and quietly selects the favourable moment, when the wasp is turning
round to enter the nest backwards, and deposits eggs on the prey. It
appears from Fabre's account that the Bembex is well aware of the
presence of the fly, and would seem to entertain a great dread of it,
as if conscious that it is a formidable enemy; nevertheless the wasp
never attacks the little fly, but allows it sooner or later to accomplish
its purpose, and will, it appears, even continue to feed the fly-larvae,
though they are the certain destroyers of its own young, thus
repeating the relations between cuckoo and sparrow. Most of us
think the wasp stupid, and find its relations to the fly incredible or
contemptible. Fabre takes a contrary view, and looks on it as a
superior Uncle Toby. We sympathise with the charming French
naturalist, without forming an opinion.
Doubtless there are many other interesting features to be found in

the life-histories of Tachinidae, for in numbers they are legion. It is
probable that we may have 200 species in Britain, and in other parts
of the world they are even more abundant, about 1000 species being
known in North America.[433] The family Actiidae is at present
somewhat doubtful. According to Karsch,[434] it is a sub-family of
Tachinidae; but the fourth longitudinal vein, it appears, is straight.
Fam. 36. Dexiidae.—These Insects are distinguished from
Tachinidae by the bristle of the antennae being pubescent, and the
legs usually longer. The larvae, so far as known, are found in various
Insects, especially in Coleoptera, and have also been found in
snails. There are eleven British genera, and about a score of
species.
Fam. 37. Sarcophagidae.—Distinguished from Muscidae and

Tachinidae by little more than that the bristle of the antennae is
feathery at the base but hair-like and very fine at the tip.—
Sarcophaga carnaria is one of the commonest British Insects; it is
like the Blow-fly, though rather longer, conspicuously grey and black,
with the thorax distinctly striped, and the pulvilli very conspicuous in
the live fly. Cynomyia mortuorum is a bright blue fly rather larger than
the Blow-fly, of which it is a competitor; but in this country an
unsuccessful one. The larvae of the two Insects are found together,
and are said to be quite indistinguishable. Cynomyia is said to lay
only about half the number of eggs that the Blow-fly does, but it
appears earlier in the year, and to this is attributed the fact that it is
not altogether crowded out of existence by the more prolific
Calliphora. The species of Sarcophagidae are usually viviparous,
and one of them, Sarcophila magnifica (wohlfahrti), has the habit of
occasionally depositing its progeny in the nostrils of mammals, and
even of human beings, causing horrible sufferings and occasionally
death: it is said to be not uncommon in Europe but does not occur in
Britain. The genus Sarcophaga is numerous in species, and many of
them are beneficial. Sir Sidney Saunders found in the Troad that
Locusts were destroyed by the larvae of a Sarcophaga living in their
bodies; and Künckel has recently observed that in Algeria several
species of this genus attack Locusts and destroy large quantities by
depositing living larvae in the Orthoptera. In North America the
Army-worm is decimated by species of Sarcophaga.
Many of these Insects, when food is scarce, eat their own species
with eagerness, and it seems probable that this habit is beneficial to
the species. The parent-fly in such cases usually deposits more eggs

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Reactive polymers fundamentals and

applications : a concise guide to

Metallized and magnetic polymers chemistry and

Marine Waterborne and Water Resistant Polymers

The Chemistry of Bio-based Polymers Johannes Karl Fink

Biobased Polyols for Industrial Polymers 1st Edition

Natural Polymers for Pharmaceutical Applications Volume

Natural Polymers for Pharmaceutical Applications Volume

Conjugated polymers. Properties, processing, and

Biosynthetic Polymers for Medical Applications 1st

Johannes Karl Fink

Series Editor: Sina Ebnesajjad, PhD (sina@FluoroConsultants.com)

Recent titles in the series

Johannes Karl Fink

AMSTERDAM • BOSTON • HEIDELBERG • LONDON

Library of Congress Cataloging-in-Publication Data

British Library Cataloguing-in-Publication Data

For information on all William Andrew publications

Publisher: Matthew Deans

1. Unsaturated Polyester Resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1

1.7.11 Encapsulation of Electric and Electronic Parts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49

2.7.21 Adhesion Modification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119

3. Epoxy Resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 139

3.7.1 Development of Formulations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 189

4. Phenol/Formaldehyde Resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 225

4.5.2 Thermal Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 240

5. Urea/Formaldehyde Resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 255

5.6.3 Hydrolytic Stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 264

6. Melamine Resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 275

7. Furan Resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 287

7.2.2 Furfuryl Alcohol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 287

8.6.2 Thermal Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 311

9. Acrylic Resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 325

9.7.6 Drug Release Membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 336

10. Cyanate Ester Resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 345

11. Bismaleimide Resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 367

11.1.8 Maleimide Epoxy Monomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 370

12. Terpene Resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 403

12.5.3 Polyacrylate Hot-Melt Pressure-Sensitive Adhesives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 410

13. Cyanoacrylates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 417

14. Benzocyclobutene Resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 433

14.4.2 Optical Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 441

15. Reactive Extrusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 449

15.5.6 Medical Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 484

16. Compatibilization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 497

16.5.19 Solid Polymer Electrolytes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 521

17. Rheology Control . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 547

18. Grafting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 563

18.6 Special Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 589

19. Acrylic Dental Fillers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 601

20. Toners . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 629

20.3.5 Biobased Polyesters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 632

Unsaturated polyester resins consist of two polymers, 1.2.1 Monomers for an

Reactive Polymers: Fundamentals and Applications. http://dx.doi.org/10.1016/B978-0-12-814509-8.00001-4

Table 1.1 Monomers for Unsaturated Polyesters

Saturated alcohols Remarks

pounds and may be components of fiber reinforced

1.2.1.2 Acid and Anhydride Components