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Handbook of Thermoset Plastics

Handbook of Thermoset Plastics

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Handbook of Thermoset Plastics

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1,863 pages
19 heures
Sortie:
Nov 28, 2013
ISBN:
9781455731091
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Livre

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Thermosetting plastics are a distinct category of plastics whose high performance, durability and reliability at high temperatures makes them suitable for specialty applications ranging from automotive and aerospace through to electronic packaging and consumer products (your melamine kitchen worktop is a thermoset resin!). Recent developments in thermoset plastics technology and processes has broadened their use exponentially over recent years, and these developments continue: in November 2011, French scientists created a new lightweight thermoset that is as strong and stable as previous materials yet can be easily reworked and reshaped when heated which makes it unique amongst thermosets and allows for repair and recycling.

The Handbook of Thermoset Plastics, now in its Third edition, provides a comprehensive survey of the chemical processes, manufacturing techniques and design properties of each polymer, along with their applications. Written by a team of highly experienced practitioners, the practical implications of using thermoset plastics are presented – both their strengths and weaknesses. The data and descriptions presented here enable engineers, scientists and technicians to form judgments and take action on the basis of informed analysis. The aim of the book is to help the reader to make the right decision and take the correct action – avoiding the pitfalls the authors’ experience has uncovered.

The new edition has been updated throughout to reflect current practice in manufacturing and processing, featuring:

  • Case Studies to demonstrate how particular properties make different polymers suitable for different applications, as well as covering end-use and safety considerations
  • A new chapter on using nanoparticles to enhance thermal and mechanical properties
  • A new chapter describing new materials based on renewable resources (such as soy-based thermoset plastics)
  • A new chapter covering recent developments and potential future technologies such as new catalysts for Controlled Radical Polymerization
  • Goodman and Dodiuk-Kenig provide a comprehensive reference guide to the chemistry, manufacturing and applications of thermosets
  • Updated to include recent developments in manufacturing – from biopolymers to nanocomposites
  • Case Studies illustrate applications of key thermoset plastics
Sortie:
Nov 28, 2013
ISBN:
9781455731091
Format:
Livre

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Handbook of Thermoset Plastics - Elsevier Science

Handbook of Thermoset Plastics

Third Edition

Edited by

Hanna Dodiuk

Sidney H. Goodman

PDL HANDBOOK SERIES

Table of Contents

Cover image

Title page

Copyright

Dedication

Preface

Acknowledgments

About the Editors

List of Contributors

1. Introduction

History

Definitions

Cross-Linking and Curing

Influence of Time, Temperature, and Mass

Shelf Life and Pot Life

Curing

Staging

Stoichiometric Considerations

Prepolymerization and Adducting

References

Further Reading

2. Phenol–Formaldehydes

Introduction

Raw Materials

Phenol

Resinification (Production) of Phenol–Formaldehyde Resins

Phenolic Resins in Friction Materials

References

Further Reading

3. Polybenzoxazine–new generation phenolics

Introduction

Synthesis of Benzoxazine Monomers (BZ)

Ring-Opening Polymerization of Benzoxazines

Regioselectivity and Cross-Linked Structure

Inter/Intramolecular H-Bonding

Kinetics of Thermal Cure

Structure-Property Relationships

Blends/Composites of Polybenzoxazines

Green Chemistry Approaches in PBZ

Click Chemistry in PBZ

Stability and Degradation

Outlook

Acknowledgments

References

4. Aminos

Introduction

Raw Materials

Chemistry of UF Resins: Urea–Formaldehyde Condensation

Chemistry of MF Resins: Melamine–Formaldehyde Condensation

General Principles of Manufacture and Application

Applications of Amino Resins

References

5. Furans

Introduction

Resins from Furfuryl Alcohol and Furfural

Photocross-Linkable Furan Polyesters

Furan Polyurethane Foams

Photoresists from Pending Furan Chromophores

Ion-Exchange Resins Based on 2-Vinylfuran

Networks Based on Diels-Alder Polycondensations

References

6. Unsaturated Polyesters and Vinyl Esters

Unsaturated Polyesters

Vinyl Ester Resins

Compounding of Unsaturated Polyester and Vinyl Ester Resins

Property Modification of Unsaturated Polyesters

Applicable Manufacturing Processes

References

7. Allyls

Introduction

Polydiallyldiglycolcarbonate (CR-39)

Polydiallyl Phthalates

References

8. Epoxies

Introduction

Detailed Chemistry

Characterization of Epoxies

Applications

References

Further Reading

9. Polyurethanes

Introduction

General Characteristics of Polyurethanes

Raw Materials Used in the Synthesis of Cross-Linked Polyurethanes

Synthesis and Cross-Linking Reactions of Polyurethanes

Morphology of Linear/Branched vs. Cross-Linked Polyurethanes

Manufacturing Methods and Technical and Functional Properties of Thermosetting Polyurethanes

References

10. High-Performance Polyimides and High Temperature Resistant Polymers

Historical Perspective

Polyimides from Condensation Reactions

Thermoplastic Polyimides

Addition-Curable Polyimides and Other Polymers

Nadimide-Terminated Thermosetting Polyimides

Maleimide-Terminated Thermosetting Polyimides

Cyanate-Terminated Thermosetting Polymers

High-Temperature Thermosetting Resins Based on Phthalonitrile

Acetylene-Terminated Thermosetting Polymers

Propargyl-Terminated Oligomers

Phenylethynyl-Terminated Thermosetting Polymers

Applicability of Thermoset Isoimides/Imides to Resin Transfer Molding Processing

Galvanic Corrosion Resistance of Polyimide Composites

High-Performance Polymers for Lightning Strike Protection

Ultrahigh Temperature Resistant Polymers

Chemical Structures Suitable for Ultrahigh Temperature Use

Novel Cross–Linking Mechanisms for Stability at Ultrahigh Temperatures

Thermosets as Dielectric Interlayers in Integrated Circuit (IC) Fabrication

Polymer-Ceramic Materials

Acknowledgments

References

Further Reading

11. Cyanate Esters

Introduction

Chemistry

Characterization and Reaction Monitoring

Processing of Cyanate Ester Resins

Properties of Cyanate Esters

Properties of Cyanate Ester Blends with Epoxy and BMI

Recent Developments

Applications

Trade Names

References

12. Maleimide-Based Alder-Enes

Introduction to Bismaleimides

Maleimide-Based Alder-Ene Polymers

Alder-Ene Polymers from Various Allyl-Maleimide Compounds

Alder-Ene Polymer Blends

Nano-Modified Alder-Ene Polymers

Shape Memory Alder-Ene Polymers

Kinetics of Alder-Ene Polymerization

Outlook

Acknowledgments

References

13. Syntactic Foams

Introduction

Syntactic Foams Based on Thermosets

Recent Advances in Syntactic Foams

Applications of Syntactic Foams

Outlook

Acknowledgments

References

14. Silicones

Introduction

Silicone Elastomers

Silicone Laminates

Silicones in the Medical Device Industry

Special Silicones

Silicone Fluids

Other Fluid Types/Copolymers

References

15. Biobased Thermosets

Polymers from Renewable Sources

Determination of Bio-Based Content in Polymers

Raw Materials for Renewable Sources Polymers

Thermoset from Renewable Sources

References

16. Nanotechnology Based Thermosets

Introduction

Nanoclays

POSS

Nano Silica

Carbon Nanotubes (CNT)

Graphene and Expanded Graphite

Tungsten Disulfide

References

17. Crosslinked Thermoplastics

Introduction

Radiation Cross-Linking of Thermoplastics

Effects of Radiation Cross-Linking on Thermoplastic Polymers

Chemical Cross-Linking with Organic Peroxides

Effects of Peroxide Cross-Linking on Thermoplastic Polymers

Cross-Linking of Thermoplastics Using Silane Grafting Reagents

Effects of Silane Cross-Linking on Thermoplastic Polymers

Comparison of Cross-Linking Methods

Applications of Cross-Linked Thermoplastics

References

18. Processing

Introduction

Processing of Monomers: Online Monitoring of Resin Synthesis

Processing of Pre-Polymers: Online Monitoring of Resin Flow and Resin Cure During Composite Manufacture

References

Appendix. Polybenzoxazines – Commercial Information

Commercial Benzoxazine Marketed by Huntsman

Products by Henkel

Index

Copyright

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Dedication

Hanna Dodiuk

To the memory of my late mother, Miriam Auerbach, Shindler's List and Holocaust survivor, who taught me to love life in all circumstances.

Sidney H. Goodman

To Rose and Solomon Goodman, who taught me the meaning of scholarship and hard work.

Preface

Prof. Hanna Dodiuk

Head of Polymers and Plastics Engineering, Pernick Faculty of Engineering, Shenkar College of Engineering, Design and Art, Ramat-Gan, Israel

This third edition contains selected chapters on various thermoset materials, old ones and the most novel ones. The final selection of chapters in this edition was based on modern technology and applications as well as novel thermoset chemistry covering many facets of thermoset polymer science and technology as prepared by scientists and experts hailed from many corners of the globe.

The science, technology, and applications of thermosets encompass creativity and imagination, which are common in both science and art, and that serve as a locomotive to pull forward innovations in technology, materials, and products. It is for good reason that Leonardo da Vinci’s dictum – study the science of art and the art of science – is inscribed in one of the rooms in Leonardo Park in Amboise, France. The scientist visualizes the mass molecules, studies their chemical structure by advanced spectroscopic means, and then changes them according to the particular function they are meant to serve.

The advantage of plastics in general and thermoset in particular lies in its wondrous synergy with science, engineering, design, and art. Over the past few years there has been growing interest in quality plastic ware: plastic has gotten out of the ghetto of popular production, and people are inundated with colorful, sophisticated, tactilely pleasing plastic products, in prestigious design shops and design exhibitions. Focus on the material itself – by developing means of production, unusual materials, and innovative technologies – allows product designers to improve functional items and make them aesthetically valuable.

Extensive research in diverse fields – such as industry, architecture, and product design – has resulted in a more economical use of materials, coupled with enhanced functionality. Extensive engineering support, including simulations and tests of strength, provides the context for creative solutions and facilitates original design concepts.

Thermoset technology is distinctively different from the respective thermoplastic technology. The latter is somewhat simple, as the polymerization chemistry is carried out in the supplier site, while in the former case the polymerization and final molecular architecture is controlled in situ by the end user. Hence, thermoset technology has an additional degree of freedom enabling us to design the network curing density and its derived mechanical as well as thermal and physical properties.

It is difficult to imagine any contemporary product used at home, in industry, land transportation, aerospace, in the medical field or anywhere else that does not use, in some manner, a composite, an adhesive, a sealant, or a coating based on a thermoset polymeric system. New developments, e.g., chemistry, nanotechnology, encapsulation techniques, have opened up new opportunities for incorporation of new thermoset polymers.

This third edition contains 18 chapters, covering all thermosets resins, from the oldest to the novel ones, including their chemistry, properties, and applications. The structure-process-property relationships are described followed by relevant examples. The novel directions in nanotechnology, the trend in renewable sources, and new thermosets resins are described in specific chapters as well as novel processing and characterization methods specifically for thermoset resins. It should be noted that the contents are very current as the authors were asked not only to revise but also to update their articles according to the latest trends in 2013. Consequently, the chapters in this book offer insight into recent developments and perspectives on many significant ramifications of thermoset polymers science and technology. Hence, this text should be of interest to individuals engaged and/or interested in the world of thermosets in academia, government research laboratories, a variety of industries, and other research institutes. Thus the value to the engineer, technician, or scientist continues to be as a comprehensive overview, a place to get started and continue in thermoset polymers. To those practicing the trade, the new information will augment that which is known and offer fresh concepts for consideration as you ponder the solution to the next problem or design.

The 18 chapters written by world-renowned researchers have been updated as follows:

Chapters 1 and 18: revised introduction and novel processing and characterization methods.

Chapters 2, 3, and 4: revised the amino as well as the phenol resins and shed light on the new generations based on polybenzooxazine resins.

Chapters 5, 6, and 7: revised the old and added novel polyester, vinyl ester, allyls, and furan resins.

Chapters 8 and 9: revised the most popular epoxy and polyurethane resins.

Chapters 10, 11, and 12: cover elevated temperature thermoset resins, polyimides, cyanate esters, and the novel maleimide based alder-ene resins.

Chapters 13 and 14: revised the silicones as well as the syntactic foams based thermoset resins.

Chapters 15 and 16: cover the trend of using renewable sources resins for bio-based thermoset resins and summarizes the nanotechnology trends in the field.

Chapter 17: revised the cross-linking of thermoplastic resins.

I would like to take this opportunity to describe my personal approach to thermosets polymers. More than three decades ago, after my Ph.D. and post-doctoral, I joined the Israel MOD (Ministry Of Defense) research laboratories. My scientific background was physical organic chemistry, especially photo physical behavior of novel fluorescent probes for biological systems. I had no experience and no know-how in thermoset polymers.

During the first years in the laboratory, I joined the adhesion and encapsulation group where I had to study various systems using thermoset adhesives, encapsulation resins, and coatings. One of my colleagues made an enthusiastic presentation about epoxy. However, when I wondered and asked about the exact chemical structure, synthesis, characterizations, and predicted properties for longer times he could not answer me. I began to search the literature and the only book I could find at the beginning of the 80s was the first edition of this Handbook.

For the first years I worked in nearly all phases of thermoset technology, expanding into urethanes, taught about phenolic, polyesters, silicones, and polyimides, and other thermosets. Throughout this time I was always conscious of thermoset technology’s significant role in the plastics industry.

After joining the academia (mid 90s) and trying to teach students in Plastics Engineering the chemistry and properties and curing processes as well as characterization I found it very difficult since no good textbook existed and most data was either commercial or kept confidential. The detailed syntheses as well as resultant chemical structures were not known. I had to study it in order to be able to tailor specific properties for specific needs and requirements.

With time, however, the plastics industry has so burgeoned that its technology and technologists have elucidated the importance of thermosets. Production figures continuously define unsaturated polyesters, urethanes, and epoxies as major commercial entities. The technical base has largely grown, accompanied by significant theoretical understanding of the chemical processes, manufacturing techniques, and design of properties. In short, there is more science and less black magic involved today.

Consequently, after three decades of research and development in the industry and academia I felt that this was the time to revise and refresh the second edition and to prepare the most updated third edition of thermoset chemistry, processing as well as applications. When Elsevier approached me I agreed to take part and to lead this effort.

Although grounded in polymer chemistry and science, the papers presented here do not require expertise in these disciplines. It is sufficient for the reader to understand the general principles in the introduction i.e., learn the jargon and then can proceed to any specific chapter for the information sought. If there is to be a consistent thread throughout each chapter, it is that thermoset plastics are materials of construction, subject to strengths and weaknesses, as well as proper use and misuse. The data and descriptions presented are for engineers, scientists, technicians, and students who are routinely involved and take actions on the basis of informed analysis. It is our intent to help these readers make the right decisions and take the correct actions and thereby avoid the pitfalls our experience has uncovered.

To each of the contributors, my personal thanks for their hard work, cooperation, and enthusiasm on this project. I speak for all the contributors in thanking that small ‘army’ of support who helped with the tough parts: typing, editing, proofreading, offering suggestions: Finally, but no less important, our thanks to Elsevier and their staff for making order out of chaos and keeping us in full view of our final goal.

My special thanks to Mr. Sidney Goodman for his great contribution to the thermoset world. The two previous editions that he edited served for me as a guide and textbook for my activity in teaching students as well as my research in the academia and industry.

I hope that the third edition will serve as a guide for the future in the thermosets’ polymer world.

Acknowledgments

First, we are thankful to the officials of Elsevier and especially to Mr. Frank Hellwig for his assistance and unwavering help in bringing this book to fruition.

Our most sincere thanks are extended to the authors and reviewers for their contribution, enthusiasm, patience, and cooperation, without which this special updated edition would not have been possible.

Finally, as editors of this book we would like to extend very special thanks to our families without whose help accomplishing of this task would have been very difficult …

Hanna: My work on this book would not have been possible without on going support of my family to whom I am dedicating this book together with my deepest thanks for their help, when needed at difficult times and their thorough understanding for this commitment: my husband and colleague Prof. Sam Kenig, my dear daughters, Lani Dodiuk-Questembert, Attorney at Law, and medical doctor Roni Dodiuk-Gad, and the joy from my grandchildren, Jonathan, Coral, and Daria who always bring a refreshing view of the world.

Sid: I join Dr. Dodiuk in acknowledging the efforts of the Elsevier editors and staff as well as our families and colleagues for their continuing support throughout this project.

To Isao Shimoyama and Abe Landis, my close friends and past contributors, I will always miss you.

To Doris, my gratitude for never letting me forget how dull my life could have been.

About the Editors

Prof. Hanna Dodiuk

Prof. Hanna Dodiuk graduated in 1970, received her MSc in 1973 and PhD in 1977, all with honors, in Chemistry from Tel–Aviv University, Israel.

She joined the Israeli Armament Development Authority (ADA) in 1979. In 1981 was appointed as Head of the Adhesion Group in the Materials and Processes Department.

During 1986–1987 she spent a sabbatical year as a Visiting Professor at the Polytechnic University of New York, USA, in the Polymer Research Institute.

Since September 1991 until June 1997 Dr. Dodiuk held the position of Director of Materials and Processes Department in ADA. During 1997–1999 she spent sabbatical in HPM Company in Los Angeles/US and as a visiting scientist in Bayer AG, Leverkusen/Germany.

Prof Dodiuk was the president of the Israeli Polymers &; Plastics Society during 1998–2000 and was nominated as honorary fellow in 2013. She serves as a representative and expert evaluator on the European Community’s R&D Grants within Frameworks 4–7. In 2005 she served as a member of Nanotechnology advisory board of Triton Systems Inc. USA and a visiting Professor in New-Jersey Institute of Technology, Newark, USA. In 2013 she spent short sabbatical as a visiting professor at UMASS Lowell, Center for High-Rate Nanomanufacturing, USA.

Prof. Dodiuk joined Shenkar College of Engineering and Design in 1997 where she was appointed the head of Polymers and Plastics Engineering Department in 2006.

Prof. Dodiuk specializes in the areas of adhesion and adhesives science and technology, characterization and formulation of polymer adhesives, polymer composites, renewable polymers, biopolymers, dendrimers and hyperbranched polymers, special coating (super hydrophobic and super hydrophilic), surface and interfaces analysis, nanotechnology and aging of polymeric materials.

Prof. Dodiuk is author and co-author of 130 scientific publications 15 patents and editor of two books. She delivered numerous (160) lectures and conference contributions in Europe, USA, Australia and Japan. Prof. Dodiuk is a member of the Editorial Board of the International Journal of Adhesion Science and Technology and Reviews of Adhesion and Adhesives.

Sidney H. Goodman

Mr. Goodman received his Bachelor’s Degree in Chemical Engineering from the University of Illinois in 1960. He then was awarded a Master’s Degree in Chemical Engineering in 1970 from the University of Southern California, where he studied Plastics and Rubber Technology. In 1976 he was awarded a Lady Davis Fellowship at the Technion, Israel Institute of Technology, in Haifa.

Mr. Goodman started his industrial career with Jones Dabney Co., one of the few early manufacturers of epoxy resins and curatives. He later moved to California where he worked as a Product Engineer for an epoxy formulator. He then joined Applied Plastics Co. where he eventually became Plant Manager over the development and manufacturer of polymer formulations for electronic encapsulation, adhesives, flooring, tooling and molding compounds.

Mr. Goodman joined Hughes Aircraft Co. (now Raytheon, Inc) in 1977. He progressed from development engineer through line and program management responsible for programs for the US Air Force, Navy, Army, NASA and DOE, as well as major technology transfers with General Motors. Mr. Goodman retired from Hughes as a Senior Engineering Fellow. During this time he taught Plastics material and processes courses as a Senior Lecturer at the University of Southern California Department of Chemical Engineering.

Early in Mr. Goodman’s career he also taught chemistry at the U. of Illinois and U. of Louisville. He is currently a Senior Member of the Society of Plastics Engineers, and Senior Member of the Society for the Advancement of Materials and Processes Engineering. He has participated in the Test Methods/Technical Committee of the Society of the Plastics Industry, been a member of the Modern Plastics Management Advisory Panel, Industrial Advisor to the Los Angeles Trade Technical College, and consulted for the California State Office of Competitive Technology.

Mr. Goodman is the author of many papers and presentations. He has one patent covering coating of optical fibers. Prior to co editing this Handbook, he edited and contributed to the first two editions of Handbook of Thermoset Plastics, and was coauthor of Handbook of Plastics Materials and Processes. Since he retired he has published four short stories and one children’s book with a second one in press. He has recorded/read for the sight challenged and volunteered in other charitable activities.

List of Contributors

M.N. Belgacem,     Grenoble INP-Pagora, St. Martin d’Hères, France

Witold Brostow,     Laboratory of Advanced Polymers & Optimized Materials (LAPOM), Department of Materials Science and Engineering and Department of Physics, University of North Texas, Denton TX

Hanna Dodiuk,     Pernick Faculty of Engineering, Shenkar College of Engineering and Design, Ramat-Gan, Israel

Ana Dotan,     Pernick Faculty of Engineering, Shenkar College of Engineering and Design, Ramat-Gan, Israel

A. Gandini,     Instituto de Química and Escola de Engenharia de São Carlos, Universidade de São Paulo, São Carlos, SP, Brazil

Sidney H. Goodman,     Consultant, Las Vegas, NV and Principal Engineer/Scientist (Emeritus), Raytheon/Hughes Aerospace Corp. & Senior Lecturer (Emeritus), University of Southern California

C.C. Ibeh,     LERMAB, University of Lorraine, Epinal, France and King Abdulaziz University, Jeddah, Saudi Arabia

Helena Janik,     Polymer Technology Department, Chemical Faculty, Gdansk University of Technology, Poland

Bibin John,     Lithium Ion and Fuel Cell Division, Vikram Sarabhai Space Centre, Thiruvananthapuram, India

Andreas Kandelbauer,     School of Applied Chemistry, Reutlingen University, Germany

S. Kenig,     Pernick Faculty of Engineering, Shenkar College of Engineering and Design, Ramat-Gan, Israel

Justyna Kucinska-Lipka,     Polymer Technology Department, Chemical Faculty, Gdansk University of Technology, Poland

Herfried Lammer,     Kompetenzzentrum Holz GmbH, Wood Carinthian Competence Center (W3C), Austria

Kreisler S.Y. Lau,     Chemco Systems, Inc., Redwood City, California, USA

Günter Lorenz,     School of Applied Chemistry, Reutlingen University, Germany

Uwe Müller,     Kompetenzzentrum Holz GmbH, Wood Carinthian Competence Center (W3C), Austria

Rodney F. Patterson,     School of Applied Chemistry, Reutlingen University, Germany

A. Pizzi,     LERMAB, University of Lorraine, Epinal, France and King Abdulaziz University, Jeddah, Saudi Arabia

C.P. Reghunadhan Nair,     Polymers and Special Chemicals Group, Vikram Sarabhai Space Centre, Thiruvananthapuram, India

K.S. Santhosh Kumar,     Polymers and Special Chemicals Group, Vikram Sarabhai Space Centre, Thiruvananthapuram, India

M. Satheesh Chandran,     Polymers and Special Chemicals Group, Vikram Sarabhai Space Centre, Thiruvananthapuram, India

O. Shepelev,     Israel Plastics and Rubber Center (IPRC), Shenkar College of Engineering and Design, Ramat-Gan, Israel

Maciej Sienkiewicz,     Polymer Technology Department, Chemical Faculty, Gdansk University of Technology, Poland

Gianluca Tondi,     Salzburg University of Applied Sciences, Austria

Joshua Wahrmund,     Laboratory of Advanced Polymers & Optimized Materials (LAPOM), Department of Materials Science and Engineering and Department of Physics, University of North Texas, Denton TX

Oscar Zaske,     Consultant, Palos Verdes Estates, CA and Principal Engineer/Scientist (Emeritus), Raytheon/Hughes Aerospace Corp. & Senior Lecturer (Emeritus), University of Southern California

1

Introduction

Hanna Dodiuk* and Sidney H. Goodman†,    *The Pernick Faculty of Engineering, Shenkar College of Engineering and Design, Ramat-Gan, Israel,    †Principal Engineer/Scientist (Emeritus), Raytheon/Hughes Aerospace Corp. & Senior Lecturer (Emeritus), University of Southern California

This chapter presents common concepts applicable to the entire field of thermosetting plastics. Included are basic definitions and terminology, chemical reaction mechanisms, and selected analysis techniques.

Keywords

Thermoset; Thermosetting; Cross-Linking; Curing and Staging; Functionality and Stoichiometry; Cross-Link Density

Outline

History

Definitions

Cross-Linking and Curing

Influence of Time, Temperature, and Mass

Shelf Life and Pot Life

Curing

Staging

Stoichiometric Considerations

Prepolymerization and Adducting

References

This book presents an overview of a major class of materials of construction: thermosetting plastics. Using the biological analogy, this class fits into the family of materials as shown in Figure 1.1.

Figure 1.1 Relationship of thermosets in chemistry.

One popular definition of thermosets is:

…a polymeric material which can be formed by the application of heat and pressure, but as a result of a chemical reaction, permanently cross-links and cannot be reformed upon further application of heat and pressure (Schwartz and Goodman, p 9) [1].

Another more rigorous definition is found in Whittington’s Dictionary of Plastics (p 239) [2]:

Resin or plastic compounds which in their final state as finished articles are substantially infusible and insoluble. Thermosetting resins are often liquid at some stage in their manufacture or processing, which are cured by heat, catalysis, or other chemical means. After being fully cured, thermosets cannot be resoftened by heat. Some plastics which are normally thermoplastic can be made thermosetting by means of cross-linking with other materials.

This leads to an interesting concept. All too often trade usage confers titles on classes of materials. These titles reflect a nomenclature or jargon that is fully comprehensible to those in the trade. Those new to the trade soon learn the meaning of the terms by association, osmosis, etc. At some point in the technology maturation, someone decides to establish a precise definition of the terms. The true definitions are quickly found to be elusive: no two practitioners define them exactly the same way: the definitions are not scientific enough, more exceptions to the rule exist than examples of the rule, and on and on. The term thermoset or thermosetting plastics is a classic illustration of this phenomenon.

This book is an attempt to collate and present the current practices and technology associated with a group of commercial polymeric materials called Thermosets. Everyone who works with these materials has an intuitive understanding of the types of plastics that fall into this category. We know, for example, that chemical cross-linking must occur in order for the resultant product to be called a thermoset. We know that the monomeric precursors may or may not be polymeric in and of themselves, will undergo reaction when the chemical kinetics are right, and that these precursors are commonly called thermoset resins because they will participate in a cross-linking reaction.

We also know that under the right conditions many of these resins can polymerize linearly and form a traditional thermoplastic polymer. Vulcanization is a form of cross-linking wherein a rubber is formed, yet rarely do technologists refer to rubber as a thermoset plastic. Biopolymers (amino acid/protein based) are known to cross-link (one theory suggests this as a root cause of aging) and we hardly think of animals as thermosetting plastics.

This book is then structured based on the commonly perceived definitions of thermosetting resins. Both definitions stated earlier remain valid and useful.

This introductory chapter includes a series of basic terms and definitions that will be referred to throughout the individual chapters that follow. Many of the definitions will in fact be descriptions of the phenomena that best illustrate the sense of the terms, as opposed to a rigorous definition per se. That these explanations are common usage or trade jargon, that they are not scientifically precise, does not compromise or lessen their meaning or value.

History

Goodyear’s (and Hancock in England) discovery of the vulcanization of natural rubber in 1839 could be construed as the first successful commercial venture based on thermosetting polymers. The plastics industry dates the beginning of thermosetting plastics to the development of phenolics by Leo Baekeland in 1909. In this instance, Baekeland not only produced the first synthetic cross-linked polymer, but as importantly, he discovered the molding process that enabled him to produce homogeneous useful articles of commerce. The Bakelite product line dominated plastics technology for years until the advent of alkyds in 1926 and the aminos in 1928. Table 1.1 lists a synopsis of the various historical milestones in thermosetting resin technology. Progress was made more often as a result of the economical commercialization of key precursor materials rather than as a conscientious result of a chemist’s ability to tailor polymers for specific properties and characteristics. It must be remembered that the acceptance of Staudinger’s heretical concept of macromolecules was not universally accepted until the late 1920s and early 1930s, long after products made from polymeric materials had reached commercial maturity.

Table 1.1

Historical Milestones of Thermosets [3,4]

Definitions

The broad classifications of plastics – general purpose, engineering, and specialty – applies to thermosets as well as thermoplastics. General purpose thermosets are characterized by average (for thermosets) mechanical properties, lower resistance to temperature, higher coefficients of expansion, and low cost/commodity-like production and sales (tons/year). Engineering thermosets have higher mechanical properties and temperature resistance and they are perceived to be more durable. They are more expensive and have a moderate production volume (pounds/year). High-temperature thermosets can resist temperatures>400°F, often for long periods of time, yet maintain their strength, adhesive, thermal, and electrical resistance properties. Costs are often higher and manufacturing methods can be quite complex. Specialty thermosets are useful because of one or more highly specific and unusual property that offsets any lack of other good properties. They are usually very expensive and are produced in relatively small quantities (pounds/batch). Overlapping between the three categories often occurs; a general purpose phenolic is often competitive with an engineering polyimide. The individual families of plastics in this book can be loosely classed as shown in Table 1.2.

Table 1.2

Categories of Thermosets

It is assumed that the reader has a reasonable understanding of the basic principles of polymer science and organic chemistry. These initial discussions are therefore designed to highlight and review some of the basic concepts in order to establish the proper perspective for the material which follows.

Cross-Linking and Curing

A linear polymer is a long continuous chain of carbon–carbon bonds with the remaining two valence bonds attached primarily to hydrogen or another relatively small hydrocarbon moiety. Figure 1.2 shows a schematic representation of some linear polymer configurations.

Figure 1.2 Simplified representation of various linear polymer configurations [1].

A network polymer is formed as a result of the chemical interaction between linear polymer chains or the build-up from monomeric resinous reactants of a three-dimensional fish-net configuration (Figures 1.3(a) and 1.3(b)). The process of interaction is called cross-linking and is the main distinguishing element of a thermosetting material. The thermo implies that the cross-linking proceeds through the influence of heat energy input, although, as will be seen in the individual chapters, much cross-linking occurs at room temperature (25°C, 77°F) and below. In recent years, some researchers have chosen to describe thermosets that cross-link at or below room temperature as "chemosets," although this term has not been universally accepted. The setting term references the fact that an irreversible reaction has occurred on a macro scale. The network polymer formed has an infinite molecular weight with chemical interconnects that restrict long-chain macromovement or slippage.

Figure 1.3 (a) Lightly cross-linked network polymer. (b) Highly cross-linked network polymer.

Molecular functionality (i.e. number of reactive moieties per mole of reactant) dictates the potential for a cross-linking reaction. A total average functionality between reactant elements greater than two suggests the potential for cross-linking independent of mechanism. In other words, the bifunctional C=C would, via an addition reaction, normally produce a linear polymer. If, however, other unsaturation is generated or remains in the formed linear chain, cross-linking can still occur (Figure 1.4).

Figure 1.4 Linear chain formation and cross-linking via addition polymerization.

Similarly for a condensation reaction, a tri- or polyfunctional reactant will form a thermoset structure with a polyfunctional comonomer (Figure 1.5).

Figure 1.5 Linear chain formation and cross-linking via condensation polymerization.

Influence of Time, Temperature, and Mass

The temperature dependency of cross-linking reactions, for all intents and purposes, behaves in a traditional Arrhenius relationship. Thus ambient temperature strongly influences cross-linking rate. Since all commercial thermosetting reactions are exothermic, a mass effect also influences the rate of reaction. Monomer concentration effects are generally associated with stoichiometric balances between reactants as well as the normal free volume accessibility of each of the reactants to each other.

Perceptually, it is easier to describe the events of cross-linking if we focus on the reaction between two low-viscosity liquids. The principles, however, are valid whether the monomers are solids, liquids, gases, or mixtures thereof.

Referring to Figure 1.6, we can track a polymerizing mixture of monomers by observing the viscosity change versus time at a given temperature. Beginning at t0, the mixture has a viscosity η0. The heat generated from the exothermic reaction produces a typical viscosity decrease (η1). As the molecular weight of the mass increases, the resultant mixed viscosity increase outpaces and quickly surpasses any reduction caused by heat. The molecular growth continues over time until a perceptible macroscopic gel-like lump can be sensed. This is tgel the gel point, or more commonly, the gel time.

Figure 1.6 Viscosity vs. time at constant temperature for a liquid thermosetting system.

From this point forward the viscosity goes to infinity. In other words, the polymeric mass becomes a macroscopic solid: a plastic. In some liquid systems the knee in the curve at the gel time is hard to identify because the viscosity increase is very gradual over time. With solid molding powders, pressure and heat must be applied in order to generate a fluid condition so that the gel time can be determined.

Usually a wooden probe is sufficient to detect the gel point with a good deal of accuracy (±0.5 minutes). Sophisticated equipment is available that automatically measures the gel point based on the length of flow of a molding powder, the increase in torque of an oscillating rubber-like mass, the change in dielectric constant of the cross-linking mass, as well as many other parameters. However measured, accuracy of less than minutes is rarely required.

The term most frequently used in the trade for this gelling phenomenon is curing. To cure a thermoset is to cause it to cross-link. Vulcanization is the rubber industry’s term for curing.

Typically, the coreactant monomers are referred to as the resin and curing agent. The resin is the resinous monomer from which the family name is derived (e.g. an epoxy plastic is an epoxy resin that has been cross-linked). The curing agent is the coreactant and goes by many names: curative, curing agent, hardener, catalyst, Part B, etc.

Any cross-linking reaction is influenced by temperature. As the ambient temperature increases, the rate of reaction increases. Additionally, these reactions are exothermic. Since all polymers are inherently thermal insulators, the exothermic heat cannot easily leave the curing mass and thus adds to the heat input for continued reaction. Figure 1.7 demonstrates this effect. Curve 1 represents a normal room temperature cure similar to Figure 1.6. With added heat (T2>T1, Curve 2) the gel time decreases. Curve 3 (T3latent condition are called one-can or single-package systems. This latent storage is normally desired at room temperature although many applications can conveniently deal with refrigerated or frozen storage.

Figure 1.7 Influence of ambient cure temperature on the gel time of thermosets.

This latency can be useful in other ways. Resinous mixtures can be applied to supporting films or impregnated into cloth fabrics and then stored in their latent conditions. This is particularly useful in adhesive and laminating applications. The distinction between so-called hot-melt systems and latent one-can thermosets must be emphasized. The former are generally solid thermoplastics that can be liquefied by melting. When coated on a film they return to a stable solid state. Latent thermosets are reactive. Whether applied to a surface from solution or as a melted liquid, the reaction will initiate and proceed as a function of ambient temperature conditions. In other words, they have a finite shelf life (see definition below). The colder the storage conditions, the more extended the latency. Another process, upstaging, is different from these two conditions and will be discussed in more detail shortly.

The mass effect on gelation parallels the temperature effect. As a cross-linking mass increases in size, the ability to transfer the exothermically generated heat away from the reaction site decreases significantly because of the thermally insulative nature of polymers. Curve A in Figure 1.8 shows the typical gel profile for a given mass. Curve B represents the doubling of the mass, whereas curve C represents a halving of the mass (no Arrhenius relationship is suggested by doubling or halving). Curve D describes a condition where the mass is below some critical threshold size that arrests the cross-linking and generates an effective latency.

Figure 1.8 Influence of mass on the gel time of thermosets.

In practical terms, the temperature/mass dependency is very significant. For example, a 5-gallon mix of a urethane flooring varnish compound may gel in 20 to 30 minutes with an often violent exotherm. However, if the same mass is poured and spread over a cold floor within a few minutes of mixing, the gel time may extend itself to 4 to 8 hours. Similarly, an adhesive bonding two dissimilar metals will take longer to gel than if it is bonding two pieces of plastic: the metal acting as a heat sink, the plastic acting as an insulator.

Shelf Life and Pot Life

Shelf life is an arbitrary time for practical storage of a thermoset system. Shelf life derives from the storage concept. In other words, how long can a thermoset be left on the shelf before it becomes difficult or even impossible to use in the intended application? The term can refer to a one-can system (e.g. a phenolic molding compound must be molded within 1 year of compounding) or a two-can mix that must be set aside for a few hours before use. Shelf life is also used to describe the storage stability of unmixed components of a thermosetting resin system if there is some threat to their reactivity as a consequence of the storage. For example, some curing agents are very hygroscopic and will lose reactivity if airborne moisture were to penetrate the storage container.

Working life, or pot life, is the available time to process a reacting thermosetting formula. Once the ambient cure temperature is reached and the cross-linking reaction begins, pot life describes the time available before the mixture becomes intractable or otherwise difficult to process. For example, the pot life of a coating is the time during which the viscosity remains low enough to allow for easy brushing or spraying. In a molding compound, the working life represents the amount of residence time available in the molding machine before the material must be injected into the mold in order to have trouble-free molding and/or a defect-free part.

Curing

The establishment of a sequence of time, temperature, and pressure needed to produce a thermoset part is the cure schedule. A simple example of one such schedule is that found on tubes of household epoxy glue. Here residence at room temperature for 16 to 24 hours under slight contact pressure clearly defines the conditions needed to affect a sufficient bond. An example of the other extreme, an extended, highly specialized schedule established for a polybenzimidazole laminate is shown in Table 1.3.

Table 1.3

Typical Processing Schedule for a Polybenzimidazole Laminate

Expose laminate prepreg in a press to 120°C with pressure increasing from contact to 200 psi. Increase temperature to 370°C and hold for 3 hours. Cool to 100°C, remove from press, and post-cure under dry N2 or vacuum as follows:

24 hours at 315°C

24 hours at 345°C

24 hours at 370°C

24 hours at 400°C

8 hours at 425°C

3 hours at 370°C in air

In a multi-step curing sequence, the gel point most often occurs in the very early stages. From an efficient producibility point of view, the sooner a part can be handled after forming the better. This frees up the more expensive molding equipment and allows the cure to reach completion (post-curing) in a relatively low-cost environment (e.g. an oven). The criteria used to establish this point are generally sufficient green strength of the part (can be handled without deformation) and sufficient cure to minimize shrinkage (very little shrinkage stress or warpage will set in beyond this point).

A cure schedule is derived by plotting the change in the plastics’ properties of interest against time at temperature and pressure. A sample curve is generated like the one shown in Figure 1.9. Practical considerations generally dictate that the cure time be chosen at some fractional level of the ultimate properties. This is because the time scale can often be logarithmic. Thus 90% of, say, ultimate tensile strength, may be achieved in a few hours at 25°C. The remaining 10% (often not needed for use) may require months to years for achievement.

Figure 1.9 Mechanical property of a thermosetting polymer vs. time.

Where more than one plastics property is important the cure schedule must reflect a reasonable time-temperature-pressure relationship that will yield an optimized combination of properties. Figure 1.10 describes such a circumstance. A thermoset formulator must be aware of all these considerations in his design of a useful compound. In addition, heat-up and cool-down rates, volatiles release, part design, and many other factors influence the cure sequence ultimately designated to produce a part. An example of a ramped cure schedule for a polyimide composite is shown in Figure 1.11.

Figure 1.10 Optimization of cure schedule for thermosetting plastics. Optimum properties occur at point A.

Figure 1.11 Autoclave cure cycle used for typical polyimide composite [5].

Staging

The influence of temperature on curing generates another practical production control. This is the concept of staging. The thermoset formula when first mixed (cross-linking has effectively not begun) is called the A-stage. As time, and thus cross-linking, progresses, the compound goes through the B-stage. This is a time line as shown Figure 1.12.

Figure 1.12 Staging time line for thermosets.

Many thermosets can have the reaction arrested at any point along this line. The simplest way to do this is to drop the temperature sufficiently below the reaction temperature to a point of latency. Depending on conditions, this latency period can be quite long (not uncommonly 6 to 24 months at room temperature and lower).

In addition, the polymer/monomer mixture at this point may well change its physical state to a more useful form. For example, a B-staged phenolic molding powder will harden and embrittle compared to the A-stage. It can be frangibly crushed into a non-sticking, free-flowing powder that is stable at room temperature for 12 or more months. Epoxy resins can be coated while liquid on a polymeric carrier film, B-staged to a fixed degree of tackiness, and stored under refrigeration for 6 to 12 months. This provides a useful tape-supported adhesive that only requires application to a substrate and subsequent heating for bonding.

The C-stage represents the fully cross-linked part in its final configuration.

Cross-Link Density

Cross-link density can be defined as the number of effective cross-links per unit volume of the thermoset material, in inverse relation to the molecular weight between cross-links (Mc). This parameter is influenced by numerous variables:

1. Functionality: the number of reactive functional sites on the reactants (monomers).

2. Chain length: the length between one cross-link and another.

3. Actual number of functional sites that react (depends on the process).

4. Chain mobility between cross-links (depends on the chain structure).

Cross-link density is a critical parameter that determines the properties of the cured resin, particularly the mechanical properties. Generally, a thermoset resin with high cross-link density is harder but more brittle, while low density leads to increased flexibility, better impact strength and higher elongation. Table 1.4 shows examples of this relationship.

Table 1.4

Relationship of Cross-link Density to Polymer Properties

This rule-of-thumb allows one to tailor the molecular weight between cross-links to optimize final material performance. Cross-link density, however, is not the only factor in determining resin properties of the resin (e.g., molecular structure contributes significantly to polymer morphology as well).

In summary, once the reactants (monomers) are chosen, cross-link density is dependent on the number of reactive sites that actually reacted during cure. For example, heating the curing mass increases chain mobility and causes more spatial interaction to end with a cross-link (see Figures 1.9 and 1.10). In contrast, to generate higher molecular weight between cross-links, one can: (1) alter the main reaction process by using reactants (monomers) with a large length to functionality ratio, (2) add a small percentage of nonreactive diluting agent(s) to improve molecular mobility and separation of cross-link sites, and/or (3) use mono-functional reactive molecules to react with and cap the open ends of the polymers to stop the reaction.

Measuring Cross-Link Density

There are a number of methods for measuring the cross-link density of a thermoset resin: chemical analysis, infra-red/near-infrared spectroscopy (IR), swelling, Differential Scanning Calorimetry (DSC), and parallel plate rheometry. These methods measure the extent to which the active resin sites are consumed. Other methods can measure the properties that relate directly to the cross-link density: heat distortion temperature, glass transition temperature, hardness, electrical resistivity, dynamic and mechanical properties, thermal expansion, and refractive index (see Figure 1.10 and Table 1.4).

The most common way is the use of swelling experiments because they are generally easier and lower cost to perform compared to other options.

The degree of swelling is an inverse dependency on the cross-link density of thermoset networks. The greater the cross-link density, the lower the degree of swelling.

The earliest theory to describe the cross-link density is the Flory–Rehner equation. The equation describes the average molecular weight of polymer chains between two consecutive junctions. The Flory–Rehner equation describes the mixing of polymer and liquid molecules as predicted by the equilibrium swelling theory of Flory and Rehner. It describes the equilibrium swelling of a lightly cross-linked polymer in terms of cross-link density and the quality of the solvent. The theory considers forces arising from three sources:

1. The entropy change caused by mixing of polymer and solvent.

2. The entropy change caused by reduction in numbers of possible chain conformations on swelling.

3. The heat of mixing of polymer and solvent, which may be positive, negative, or zero.

Flory–Rehner equation (Equation 1.1):

(1.1)

is the Flory solvent–polymer interaction term.

Subsequent work has led to a few evolved theories for the characterization of cross-link networks. The most accepted model is the Flory and Erman equation that includes detailed swelling–structure relationships for non-ionic networks.

, the molecular weight between cross-links, is described by the following equation (Equation 1.2):

(1.2)

=the specific volume of the polymer, V1 is the molar volume of the swelling agent, ν2m is the polymer volume fraction in the equilibrium-swollen system, ν2r is the polymer volume fraction in the relaxed state (i.e. after cross-link but before swelling), φ is the number of branches originating from a cross-link site, and χ is the Flory polymer–solvent interaction parameter (http://w3.gazi.edu.tr/web/caykara/makaleler/p31.pdf).

Differential Scanning Calorimetry (DSC) is used to predict the change of cross-link density by following the change of temperature that accompanies the chemical reaction of the curing process. The sample is heated at a programmed rate so that enough energy is provided to the potential reactive groups for reaction. The peak glass transition temperature, most often exothermic, correlates with the amount of molecules that reacted. When no peak is observed, it is accepted that all reactants (monomers) are fully cured.

The parallel plate test has great shearing ability, therefore it can be used to analyze hard thermoset resins. Like the DSC test, the parallel plate can identify additional chemical reaction by differences in the measured viscosity [6].

Stoichiometric Considerations

One of the major responsibilities of the thermoset resin chemist is to balance the coreactants stoichiometrically. He does this by establishing a mix ratio, the weight-to-weight proportion of the resins and curatives. In theory, each functional group in each monomer must react on a 1/1 molar basis. The final cross-linked plastic should have no residual reactive sites if all reactants have been properly proportioned and subjected to optimum cure conditions.

In reality, many considerations drive the polymerization process away from the ideal. To begin with, as the molecular weight of the polymerizing mass increases, it becomes sterically less possible for reacting species to come together and react. Side reactions and chain-stopping contaminants may reduce the calculated number of reactive sites. Although molecular movement never truly ceases in a cross-linked mass, the time span for complete cure (i.e. to reach ultimate properties) may be logarithmic (see earlier discussion on cure schedules).

In practice, a resin formulator will calculate a theoretical stoichiometry for his intended formula. Then he will prepare samples under a given set of cure conditions and test for the change in selected properties of the resultant plastic versus change in stoichiometric ratio. This can be a long, cumbersome, and expensive process. One shortcut common to the epoxy chemist is to run a Soxhlet extraction in acetone. A curve like the one shown in Figure 1.13 is obtained.

Figure 1.13 Optimizing mix-ratio using a Soxhlet apparatus.

Obviously that mix ratio which creates the least weight loss should represent the maximum integrity of the cured part (i.e. the best properties). Once established, the formulator can narrow his choice of mix ratios to those near this optimum and reduce the testing required to pinpoint the exact ratio that will provide the properties he is seeking. Examples of representative stoichiometric calculations can be found in the individual chapters on polyurethanes and epoxies.

Experience has demonstrated that it is not at all uncommon for mix ratios to depart from 1/1 molar by as much as 20 to 30%. The responsibility for insuring that the stoichiometric balance is maintained varies among thermoset types. The phenolic chemist is concerned during the initial manufacture of a polymer. The user need only add heat and pressure to get a part. The polyester chemist establishes the balance when he makes the base resin. He then adds his cross-linking monomer and the user catalyzes the mix to effect the cure. The epoxy and urethane chemist, on the other hand, may not only do as the others, but may also design a system that requires the end user to mix the reactants in the correct ratio. As will be described in later chapters, this may impose a significant constraint on the user to insure that the predetermined mix ratio tolerance is maintained.

Prepolymerization and Adducting

Prepolymerization is a method of increasing the molecular weight of a forming polymer to some intermediate value. Prepolymerization is often confused with B-staging. During B-staging the polymer formation is arrested at some practical intermediate point. It is a random process that yields various molecular weight moieties and some cross-linking.

A prepolymer is normally formed under precisely controlled conditions to yield a stable polymer of specific molecular weight and configuration, most often without any cross-linking. For example, an isocyanate will be coreacted with a glycol at a stoichiometric ratio much greater than 1/1. A urethane prepolymer will be formed with sufficient residual isocyanate to further react in a curing environment.

There are many reasons for generating prepolymers. Among the more prevalent are the following: increase the viscosity of monomer, decrease toxicity and/or reactivity for control of gel time and exotherm, and balance the mix ratio of a formulated system (compensate for the addition of additives and fillers).

When a monomeric resin is capped with a coreactant, the process is called adducting. The technique proceeds via the following schematic sequence:

In a direct polymerization, the two monomers will react as in Equation (1.3) (i.e. a cross-linked polymer).

(1.3)

If FA and FB are olefinic bonds, then the adducted moiety contains FAFB (i.e. C–C bonds resulting from the typical addition reaction). If FA is a carboxyl group, say, and FB is an amine, then a condensation reaction will occur yielding an amide: FAFB=–CONH, and H2O.

The adduction process proceeds as in Equation (1.4).

(1.4)

The cross-linking is completed by stoichiometrically reacting the resulting pendant FA groups with more FB-containing reactant. The net result, Equation (1.5), is a polymer with essentially the same cross-linked structure as with a standard cross-linking, Equation (1.3).

(1.5)

The reasons for adducting are essentially the same as for prepolymerization.

References

1. Schwartz SS, Goodman SH. Plastics materials and processes New York: Van Nostrand Reinhold Co.; 1982.

2. Whittington LR. Whittington’s dictionary of plastics Stamford, Connecticut: Technomic Publishing Co.; 1968.

3. SPE JOURNAL, 1967.

4. ASM Handbook, vol. 21. Composites, ASM International, 2001.

5. Delmonte J. Technology of carbon and graphite fiber composites New York: Van Nostrand Reinhold Co.; 1981.

6. Sperling LH. Introduction to physical polymer science 4th ed. Bethlehem, PA: John Wiley & Sons; 2006.

Further Reading

1. Morton M. Introduction to rubber technology New York: Reinhold Publishing Corp.; 1964.

2. Severs ET. Rheology of polymers New York: Reinhold Publishing Co.; 1967.

2

Phenol–Formaldehydes

A. Pizzi and C.C. Ibeh,    LERMAB, University of Lorraine, Epinal, France and King Abdulaziz University, Jeddah, Saudi Arabia

The chapter describes phenol-formaldehyde resins, their basic chemistry and technology, and the technology and areas of their applications.

Keywords

resins; phenol-formaldehyde; adhesives; wood; foundry cores

Outline

Introduction

Raw Materials

Phenol

Resinification (Production) of Phenol–Formaldehyde Resins

Phenolic Resins in Friction Materials

References

Introduction

A number of different thermosetting adhesives and resins are used industrially. Among these, thermosetting resins based on the use of formaldehyde-based resins obtained by polycondensation have dominated the field for many decades. Many of these are used mainly for their application to wood and wood fiber panel products of all types and for a variety of other major applications.

Formaldehyde-based thermosetting resins constitute well more than 50% by volume (NB: not by value) of all the adhesives used today in all fields. Thus, resins such as urea-formaldehyde (UF), phenol-formaldehyde (PF), melamine-formaldehyde (MF), melamine-urea-formaldehyde (MUF), resorcinol-formaldehyde, and other minor ones constitute today, with some notable exceptions, a low margin commodity produced in great quantities. The reason for such wide use is mainly their relative ease of manufacture and the relatively low plant investment necessary to produce such resins. This apparent ease belies the high technology that is in-built in such resins, newcomers to this field being easily deceived by the apparent simplicity of their chemistry and of their preparation. While their basic chemistry and technology is quite understandable, the development of applicable formulations acceptable to today’s sophisticated markets is not an easy matter.

In the form in which they are delivered, these adhesive resins are mainly liquid and consist of mainly linear or branched oligomeric and polymeric molecules in an aqueous solution; they are also partly a dispersion of molecules in these same aqueous solutions. During hardening and gelling they convert irreversibly into insoluble and non-melting three-dimensionally cross-linked networks. The hardening conditions used can be acidic (for aminoplastic resins such as those based on urea and melamine), highly alkaline or acid (phenolic resins), or neutral to light alkaline (resorcinol resins, tannins).

The consumption of resins for thermosetting formaldehyde-based wood adhesives has by far the greatest market volume in North America and Europe (1997 and 1999, respectively), based on resin solids (Table 2.1).

Table 2.1

Estimated Consumption of Wood Adhesive Resin Solids in North America and Western Europe

*1997

**1999

Other than their main application as wood panel adhesives, other major fields of application for these adhesives are as foundry cores and mold binders, and for the impregnation and bonding of paper with PF and MF resins to obtain resistant laminates. There are applications of these resins other than as adhesives, such as in preparation of rigid foams, as binders for temperature-resistance fibers for break-lining, and many others. The total worldwide production and consumption of urea-formaldehyde (UF) resins and phenolic (PF) resins for all uses is not exactly known, but is today reputed to be approximately 10–11 million tons/year for UF resin solids and 3.5–4 million tons for PF resin solids.

Form a purely technical point of view, these resins have evolved during the last few decades to yield:

• Highly reactive adhesives with quick gelling and hardening behavior and steep increases in bonding strength even at a low degree of chemical curing.

• Highly reactive adhesive mixes by inclusion of additives such as accelerators, special hardeners, cross-linkers, and others.

• Lower cost resins that maintain the same peformance, or even improve it.

• More environmentally acceptable adhesives.

Thus, the minimization of the content in expensive melamine in exterior-grade MUF-resin, the marked decrease of the content in expensive resorcinol in structural exterior-grade PRF adhesives, or the development of some fast-curing alkaline PF resols are glaring examples of these trends.

The impact of resins on various environmental aspects such as waste water and effluents and emission of noxious volatile chemicals (e.g. formaldehyde during the production of, and from, finished boards) has been an important trend in the last couple of decades, and promises to have future importance. The emission of formaldehyde was a matter of concern in the past, a problem that has now been solved. Also of concern are the effluent discharges of free phenols or other monomers.

Phenolic Resins

Phenol-formaldehyde resins (phenolic resins, PF), the first thermosetting plastics, are considered to be the first truly synthetic commercially available plastic resins. Unlike celluloids, the first man-made plastic resins, phenolic resins are made from purely synthetic materials. Today resins based on natural polyphenolic materials are starting to be used industrially, namely condensed tannin resins. Phenol-formaldehyde resins are formed by the chemical reaction between phenols and formaldehyde solutions (formalin).

Work in the area of phenols and formaldehydes began prior to the 20th century with Adolf Bayer [1] in 1872 and Losekam [2] in 1889. The first commercially available phenolic resin, called Laccain, was introduced by Blumer [2] in 1902 as a substitute for shellac; it was not a commercial success [3]. The use of phenolic resins was popularized by the heat and pressure patents [3–6] of Dr. Leo H. Baekeland in 1907; hence, he is known as the father of phenolic resins. Today, some of the most popular phenolic resins bear the trade name Bakelite in reference to the company (General

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