Chemistry and Technology of Emulsion Polymerisation E-Book

• Herausgeber: John Wiley & Sons
• Kategorie: Fachliteratur
• Sprache: Englisch

Seitenzahl: 721

Veröffentlichungsjahr: 2013

Beschreibung

Chemistry and Technology of Emulsion Polymerisation 2e provides a practical and intuitive explanation of emulsion polymerization, in combination with both conventional and controlled radical polymerization. For those working in industry,  coupling theory with everyday practice can be difficult. By carefully explaining the principles of the reaction, based on well-designed experimental investigation, the book explains how the principles relate to practical application.

The second edition of this book includes a new chapter on morphology of latex particles, a rapidly progressing area where modelling the thermodynamic and kinetic aspects of phase separation and morphology has developed into a mature and powerful tool to predict and control morphology of latex particles.

 Another area that is rapidly progressing is the application of controlled radical polymerisation in emulsion polymerization. Controlled radical polymerisation is used in aiding encapsulation of inorganic particles like pigment particles and clay platelets. These latest developments are included in the second edition.

Leseprobe

Contents

Cover

Title Page

Copyright Page

List of Contributors

Abbreviations

List of Frequently Used Symbols

Introduction to the Second Edition

Introduction to the First Edition

Chapter 1: Historic Overview

1.1 The Early Stages

1.2 The Second Half of the Twentieth Century

Chapter 2: Introduction to Radical (Co)Polymerisation

2.1 Mechanism of Free Radical Polymerisation

2.2 Rate of Polymerisation and Development of Molecular Mass Distribution

2.3 Radical Transfer Reactions

2.4 Radical Copolymerisation

2.5 Controlled Radical Polymerisation

Chapter 3: Emulsion Polymerisation

3.1 Introduction

3.2 General Aspects of Emulsion Polymerisation

3.3 Basic Principles of Emulsion Polymerisation

3.4 Particle Nucleation

3.5 Particle Growth

3.6 Ingredients in Recipes

3.7 Emulsion Copolymerisation

3.8 Particle Morphologies

Chapter 4: Emulsion Copolymerisation, Process Strategies

4.1 Introduction

4.2 Monomer Partitioning

4.3 Process Strategies

Chapter 5: Living Radical Polymerisation in Emulsion and Miniemulsion

5.1 Introduction

5.2 Living Radical Polymerisation

5.3 Nitroxide-Mediated Polymerisation in Emulsion and Miniemulsion

5.4 ATRP in Emulsion and Miniemulsion

5.5 Reversible Chain Transfer in Emulsion and Miniemulsion

5.6 Conclusion

Chapter 6: Particle Morphology

6.1 Introduction

6.2 Synthesis of Structured Polymer Particles

6.3 Two-Phase Polymer–Polymer Structured Particles

6.4 Two-Phase Polymer–Inorganic Particles

6.5 Multiphase Systems

6.6 Effect of Particle Morphology on Film Morphology

Acknowledgements

Chapter 7: Colloidal Aspects of Emulsion Polymerisation

7.1 Introduction

7.2 The Stabilisation of Colloidal Particles against Aggregation

7.3 Pair-Potentials in Colloidal Dispersions

7.4 Weak Flocculation and Phase Separation in Particulate Dispersions

7.5 Aggregate Structure and Strength

Chapter 8: Analysis of Polymer Molecules including Reaction Monitoring and Control

8.1 Sampling and Sample Handling

8.2 Monomer Conversion

8.3 Molar Mass

8.4 Chemical Composition

8.5 Detailed Molecular Characterization

Chapter 9: Particle Analysis

9.1 Introduction

9.2 Particle Size and Particle Size Distribution

9.3 Sampling

9.4 Particle Size Measurement Methods

9.5 Comparison of Methods

9.6 Particle Shape, Structure and Surface Characterisation

9.7 Discussion of the Available Techniques

Chapter 10: Large Volume Applications of Latex Polymers

10.1 Market and Manufacturing Process

10.2 Paper and Paperboard

10.3 Paints and Coatings

10.4 Adhesives

10.5 Carpet Backing

Acknowledgements

Chapter 11: Specialty Applications of Latex Polymers

11.1 Introduction

11.2 Specific Requirements for the Design of Specialty Latex Particles

11.3 Preparation Methods of Latex Particles for Specialty Applications

11.4 Applications

11.5 Conclusions

References

Index

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ISBN: 9781119953722

List of Contributors

Elena Akhmastkaya Basque Center for Applied Mathematics (BCAM), Spain

Jose M. Asua POLYMAT, University of the Basque Country UPV/EHU, Spain

Bernadette Charleux Chemistry, Catalysis, Polymers & Processes, Université de Lyon, France

Thierry Delair Laboratoire des Matériaux Polymères et des Biomatériaux, Université Claude Bernard Lyon 1, France

R. G. Gilbert Centre for Nutrition & Food Science, University of Queensland, Australia, and Tongji School of Pharmacy, Huazhong University of Science and Technology, China

Finn Knut Hansen Department of Chemistry, University of Oslo, Norway

Ola Karlsson Division of Physical Chemistry, Lund University, Sweden

Haruma Kawaguchi Graduate School of Engineering, Kanagawa University, Japan

Hans Heuts Department of Chemical Engineering & Chemistry, Eindhoven University of Technology, The Netherlands

Jose Ramon Leiza POLYMAT, University of the Basque Country UPV/EHU, Spain

Yuri Reyes Mercado POLYMAT, University of the Basque Country UPV/EHU, Spain

Jan Meuldijk Department of Chemical Engineering & Chemistry, Eindhoven University of Technology, The Netherlands

Michael J. Monteiro Australian Institute for Bioengineering and Nanotechnology, The University of Queensland, Australia

Christian Pichot Saint-Priest, France

Brigitte E.H. Schade Particle Sizing Systems, Waterman, Holland

Jürgen Schmidt-Thümmes BASF AG, GMD, Germany

Peter Schoenmakers Department of Chemical Engineering, University of Amsterdam, The Netherlands

Bernhard Schuler BASF AG, ED/DC, Germany

Dieter Urban BASF AG, GMD, Germany

A.M. van Herk Institute of Chemical and Engineering Sciences, Jurong Island, Singapore and Department of Chemical Engineering & Chemistry, Eindhoven University of Technology, The Netherlands

Brian Vincent School of Chemistry, University of Bristol, UK

Abbreviations

AAAcrylic acidABSAcrylonitrile-butadiene-styreneAerosol MAAMA, sodium di-hexyl sulfosuccinateAerosol OTAOT, sodium di(2-ethylhexyl)sulfosuccinateAFMAtomic force microscopyAIBNAzobisisobutyronitrileATRPAtom transfer radical polymerizationBButadieneBAn-Butyl acrylateBPOBenzoyl peroxydeBuna NButadiene-acrylonitrile copolymerBuna SButadiene-styrene copolymerCCAColloidal crystalline arrayCCDChemical composition distributionCDBCumyl dithiobenzoateCFMChemical force microscopyCFTCritical flocculation temperatureCMCCritical Micelle ConcentrationCMMDControl molar mass distributionCPVCCritical pigment volume concentrationCRPControlled radical polymerization techniquesCTAChain transfer agentsCVPColloid vibration potentialCyclamTetrazacyclotetradecaneDLVODerjaguin-Landau-Verwey-OverbeekDMADynamic mechanical analysisDNADesoxy nucleic acidDSCDifferential scanning calorimetryEDTAEthylene diamino tetraacetic acidEHMA2-Ethylhexyl methacrylateEPAEnvironmental Protection AgencyESAElectrokinetic sonic amplitudeESEMEnvironmental scanning electron microscopyFESEMField emission scanning electron microscopyFIB-SEMfocused ion beam SEMFFFField-flow fractionationFLGNFeeney, Lichti, Gilbert and NapperHASEHydrophobically modified alkali-swellable emulsionsHDPEHigh density polyethyleneHECHydroxy ethyl celluloseHEMA2-Hydroxyethyl methacrylateHEURHydrophobically modified ethylene oxide urethanesHICHydrophobic interaction chromatographyHPLCHigh performance liquid chromatographyHUFTHansen, Ugelstad, Fitch, and TsaiIRInfraredKKelvinLV-SEMlow voltage SEMLRPLiving radical polymerisationMAMethyl acrylateMFFTMinimum film forming temperatureMMAMethyl methacrylateMMDMolar Mass DistributionMONAMS A51-(methoxycarbonyl)eth-1-yl initiating radicalNMPNitroxide-mediated living radical polymerisationNMRNuclear magnetic resonanceNRNatural rubberOEMOriginal Equipment ManufacturerOMOptical microscopyPCHPhenyl-cyclohexenePCSPhoton correlation spectroscopyPDIPolydispersity indexPDMSPoly(dimethylsiloxane)PEOPoly(ethylene oxide)PGAPoly(glycolic acid)PHSPoly(hydroxystearic acid)PLAPoly(D, L-lactic acid)PLGAPoly(glycolic-co-lactic acid)PMMAPoly(methylmethacrylate)PNIPAMPoly(N-isopropylacrylamide)PPOPolypropylene oxidePREPersistent radical effectPSAPressure sensitive adhesivesPSDParticle size distributionPTAPhosphotungstic acidPTFEPoly tetrafluorethylenePVAcPoly(vinyl acetate)PVCPigment volume concentrationQCM-Dquartz crystal micro-balance with dissipation monitoringRAFTReversible addition fragmentation transferRCTAReversible chain transfer agentsSStyreneSAMSelf-assembled monolayerSANSSmall angle neutron scatteringSAXSSmall angle X-ray scatteringSBStyrene butadieneSBLCStyrene butadiene latex councilSBRStyrene butadiene rubberSDSSodium dodecyl sulphateSed-FFFSedimentation field-flow fractionationSEMScanning electron microscopySFMScanning force microscopySPMScanning probe microscopySRNISimultaneous reverse and normal initiationSSIMSStatic secondary ion mass spectrometrySTMScanning tunneling microscopyTEMTransmission electron microscopyTEMPO2, 2, 6, 6-Tetramethylpiperidine-l-oxylTexanol®c2, 2, 4-Trimethyl-1, 3-pentanediol-diisobutyratUAcUranyl acetateUVUltravioletVacVinyl acetateVCHVinyl-cyclohexeneVOCVolatile organic compoundWWattWet-SEMwet scanning transmission electron microscopyXPSX-ray photoelectron spectroscopyXSBCarboxylated styrene-butadiene dispersions

List of Frequently Used Symbols

aeSpecific surface area for a emulsifier molecule on a polymeric surfaceAArrhenius constant of the initiation (Ai), propagation (Ap), termination (At) and transfer (Atr)average particle diameter dn, number average diameter, ds surface average diameter, dw weight average diameter, dv volume average diameterdw/dnparticle diameter non-uniformity factorEenergy of activation for initiation (Ei), propagation (Ep), termination (Et) and transfer (Etr)fInitiator efficiencyFEfficiency factor for adsorptionΔGPartial molar free energy of droplets ΔGd, ΔGa of the aqueous phase and of the latex particles ΔGlHenthalpyΔHchange in enthalpyjcritCritical length of an oligomer at which precipitation from the aqueous phase occurskexit frequencykrate constant of the initiation (ki), propagation (kp), termination (kt) and transfer reaction (ktr)[M]concentration of monomer, [M]p concentration of monomer in the polymer particles. If this depends on quantities such as radius r, time t, etc., the recommended notation is [M(r, t, …)]p. [M]a for the monomer concentration in the aqueous phase, [M]a, sat for the saturation concentration in the aqueous phase.Maverage molar mass: number-average molar mass (Mn). weight-average molar mass (Mw),Nnumber of latex particles per unit volume of latexN nNumber of particles with n radicals per particleNAAvogadro constantnnumber of radicals in a latex particleaverage number of radicals per particlenm0initially added number of moles of monomer per unit volumenumber average degree of polymerisationRgas constantr1, 2reactivity parameters in copolymerisationrprate of polymerisation per particlererate of entry of radicals per particlertrate of termination per particlerothe radius of the unswollen micelles, vesicles and/or latex particles.RpRate of polymerisationSentropyΔSchange in EntropyTtemperatureTgglass transition temperaturettimeVvolume of monomer swollen latex particlesVmmolar volume of the monomervpvolume fraction of polymerWstability ratiowpmass fraction of polymer in the particle phasexfraction conversion of monomer to polymerxnnumber-average degree of polymerisation, xw weight-average degree of polymerisationz-merThe length of an oligomer in the aqueous phase at which surface activity occursαfate parameter (fate of excited radicals)χFlory-Huggins interaction parameterδsolubility parameter or chemical shiftpermittivityγinterfacial tensionηviscosity[η]intrinsic viscosityνkinetic chain lengthπosmotic pressureρentry frequencyρiradical flux or rate of initiation (2 kd f [I])μVolume growth factorτgtime of growth of a polymer chain

Introduction to the Second Edition

The increasing need for environmentally benign production methods for polymers has resulted in a further development and implementation of the emulsion polymerisation technique. More and more companies switch from solvent based polymer production methods to emulsion polymerisation.

Since the introduction of the first edition in 2005 the experience gained with using this book in a teaching environment, led us to this second improved edition. Besides some of the new developments we added a new chapter on latex particle morphology development as especially in this area much progress has been made and a lot of research efforts, both in academia and in industry, has been devoted to this important area. Furthermore the chapter on the use of controlled radical polymerization in latex production has been substantially updated as most of the other chapters.

Powerpoint slides of figures in this book for teaching purposes can be downloaded from http://booksupport.wiley.com by entering the book title, author or isbn.

Introduction to the First Edition

New polymerisation mechanisms like controlled radical polymerisation are combined with the emulsion polymerisation technique, encountering specific problems but also leading to interesting new possibilities in achieving special nanoscale morphologies with special properties. In the past years many people have been trained in the use of the emulsion polymerisation technique. Many courses on the BSc, MSc and the PhD level as well as special trainings for people in industry are given all over the world. Despite this no recent book exists with the purpose of supporting courses in emulsion polymerisation.

This book is aiming at MSc students, PhD students and reasonably experienced chemists in university, government or industrial laboratories, but not necessarily experts in emulsion polymerisation or the properties and applications of emulsion polymers. For this audience, which is often struggling with the theory of emulsion polymerisation kinetics, this book will explain how theory came about from well-designed experiments, making equations plausible and intuitive. Another issue experienced, especially in industry, is that coupling theory and everyday practice in latex production is really hard. This is another aim of the book; showing how theory works out in real life.

The basis for the contents of this book can be found in the course emulsion polymerisation taught for many years at the Eindhoven University of Technology in the framework of the Foundation Emulsion Polymerisation. Many people have contributed to shaping the aforementioned course and therefore laying a basis for this book: Ian Maxwell, Jenci Kurja, Janet Eleveld, Joop Ammerdorffer, Annemieke Aerdts, Bert Klumperman, Jos van der Loos and last but not least Ton German. Most of the contributors to the chapters are member of the International Polymer Colloids Group, a group of experts around the world that meet on a regular basis and form a unique platform for sharing knowledge in the field.

The book is focussing on emulsion polymerisation in combination with both conventional and controlled radical polymerisation. Except for miniemulsion polymerisation, more exotic techniques like inverse emulsion polymerisation, microemulsion polymerisation and dispersion polymerisation are not covered.

The first chapter is giving a historic overview of the understanding of emulsion polymerisation, also focussing on the solution of the kinetic equations. In the second chapter an introduction is given in the radical (co)polymerisation mechanism, explaining kinetics and the development of molecular weight and chemical composition. In chapter three the basic element of emulsion polymerisation are explained, again focussing on rate of reaction and molecular mass distributions. In chapter four, emulsion copolymerisation, process strategies are explained. In chapter five the implementation of controlled radical polymerisation mechanisms in emulsion polymerisation is discussed. In Chapter 6 the development of morphology in latex production is discussed. Colloidal aspects of emulsion polymerisation are discussed in chapter seven. In chapter eight an overview of the molecular characterization techniques of (emulsion) polymers is given whereas in chapter nine the characterization techniques available for particle size, shape and morphology are reviewed. In Chapter ten and eleven bulk and specialty applications are discussed. As much as possible the nomenclature for polymer dispersions according to IUPAC has been followed (Slomkowski, 2011).

We hope that this book will become a standard textbook in courses in emulsion polymerisation.

1

Historic Overview

Finn Knut Hansen

Department of Chemistry, University of Oslo, Norway

1.1 The Early Stages

Polymers are composed of very large molecules, each of which includes a large number of repeating structural units. The oldest and most abundant group of polymers consists of the natural polymers, such as cellulose, proteins, rubbers, and so on. One of these, natural rubber, occurs in the form of a latex, that is defined as the “viscid, milky juice secreted by the laticiferous vessels of several seed-bearing plants, notably Castillia elastica, ” and so on (Bovey et al., 1955). By far the most important natural latex is that obtained from the rubber tree Hevea brasiliensis. This tree, originally from Brazil, as may be deduced from its name, was transplanted to Malaya, Sri Lanka and the East Indies (Hauser, 1930) in 1876, and eventually has made this area the most important source of natural rubber. The latex that is obtained from the tree is usually denoted as “natural latex” and is a colloidal suspension of rubber particles stabilized by protein. The rubber content of the latex is between 32 and 38% by weight, the protein 1 to 2%, different natural sugars about 2% and about 0.5% of inorganic salts (Hauser, 1930). The rubber particles vary largely in size from quite small, circa 50 nm, up to 1–2 micrometres. The rubber latex is coagulated, washed and worked into sheets that form the basis for further industrial use.

In view of the latex origin of natural rubber, it was not surprising that, when the need for a synthetic equivalent arose, the mimicking of natural rubber latex was an obvious starting point. The effort, and great success, of making synthetic rubber by emulsion polymerisation has led to the word “latex” eventually being used to refer to a colloidal suspension of synthetic polymers, as prepared by emulsion or suspension polymerisation. Such synthetic latexes are to be distinguished from dispersion of polymers prepared by grinding the polymer with water and a dispersing agent. This chapter will treat the early stages of the “invention” and production of synthetic latexes by emulsion polymerisation from the beginning and up to the middle of the twentieth century. Several reviews and book chapters on the early developments in emulsion polymerisation have already been written, and have been a natural starting point for this text. One of the first reviews is that of Hohenstein and Mark from 1946 (Hohenstein and Mark, 1946). The following is a direct quotation from their work (reprinted from J. Polymer Sci., by permission):

The earliest observations on polymerisation of olefins and diolefins as far back as 1838 (Mark and Rafft, 1941; Regnault, 1838) refer almost entirely to the pure liquid phase and describe the gradual transition from a liquid monomer to a viscous or solid polymer under the influence of heat, light, or a catalytically active substance. The idea of using a finely divided monomer in an aqueous suspension or emulsion seems to have been first conceived, about 1910, by Hofman and Delbrück (Hofman and Delbrück, 1909, 1912) and Gottlob (Gottlob, 1913). There were two main reasons for the desire to carry out the polymerisation of various simple dienes in the presence of a diluting agent: one, the fact that the use of metallic sodium as catalyst, which was common practice at that time, led to highly heterogeneous materials and posed a rather difficult problem regarding the complete removal of the alkali metal from the final polymer. The more important incentive for the use of an aqueous system, however, were the facts that all native rubbers occur in the form of latexes and that, obviously, polymerisation in the plant takes place under mild conditions in an aqueous phase without the application of elevated temperatures and high pressures, and certainly without the use of such catalysts as metallic sodium or alkali alkyls.