In-situ Synthesis of Polymer Nanocomposites E-Book

• Herausgeber: Wiley-VCH
• Kategorie: Wissenschaft und neue Technologien
• Serie: Polymer Nano-, Micro- and Macrocomposites
• Sprache: Englisch

Seitenzahl: 622

Veröffentlichungsjahr: 2011

Beschreibung

The book series "Polymer Nano-, Micro- and Macrocomposites" provides complete and comprehensive information on all important
aspects of polymer composite research and development, including, but not limited to synthesis, filler modification, modeling, characterization as well as application and commercialization issues. Each book focuses on a particular topic and gives a balanced in-depth overview of the respective subfi eld of polymer composite science and its relation to industrial applications. With the books the readers obtain dedicated resources with information relevant to their research, thereby helping to save time and money.
In-situ intercalative polymerization in the presence of filler provides distinct advantages when compared to other nanocomposite synthesis
techniques including the possibility to polymerize a large range of thermoplastic and thermosetting polymers, improved handling of gaseous
or liquid monomers or high pressure polymerization and improved control of heat of polymerization. This volume aims to highlight these
advantages of the generation of polymer nanocomposites with a large spectrum of polymer matrices. Following an overview of the synthesis
methodologies, the text goes on to discuss the most relevant polymer materials, including polyamides, polyolefi nes, polyacrylates, polyethylenes, polyurethanes, polyesters and polyepoxides.

Leseprobe

Table of Contents

Cover

Series page

Title page

Copyright page

Preface

List of Contributors

1 In-situ Synthesis of Polymer Nanocomposites

1.1 Introduction

1.2 Synthesis Methods

1.3 In-situ Synthesis of Polymer Nanocomposites

2 Polyamide Nanocomposites by In-situ Polymerization

2.1 Introduction

2.2 Manufacturing Processes of Commercially Important Polyamides

2.3 Polyamide Nanocomposites

2.4 Conclusions

3 Polyolefin–Clay Nanocomposites by In-situ Polymerization

3.1 Introduction

3.2 Clays

3.3 In-situ Polymerization of Olefins with Coordination Catalysts Supported on Clays

4 Gas-Phase-Assisted Surface Polymerization and Thereby Preparation of Polymer Nanocomposites

4.1 Introduction

4.2 In-situ Polymerization for Nanocomposite Preparation

4.3 Characteristics of GASP

4.4 Composite Preparation by GASP

4.5 Outlook and Perspective

5 PET Clay Nanocomposites by In-situ Polymerization

5.1 Introduction

5.2 Preparation of PET/Clay Nanocomposites

5.3 Morphology of the Nanocomposites

5.4 Crystallization of the Nanocomposites

5.5 Properties of the Nanocomposites

5.6 Conclusion and Outlook

6 Control of Filler Phase Dispersion in Bio-Based Nanocomposites by In-situ Reactive Polymerization

6.1 Introduction

6.2 Background

6.3 Experimental Procedures

6.4 Results and Discussion

6.5 Conclusions

Acknowledgments

7 Polyurethane Nanocomposites by In-situ Polymerization Approach and Their Properties

7.1 Introduction

7.2 PU/Carbon Nanotube Nanocomposites (PUCNs)

7.3 PU/Clay Nanocomposites (PUCLN)

7.4 PU/Functionalized Graphene Nanocomposites (PUFGNs)

7.5 Prospective of PUNs

8 In-situ Synthesis and Properties of Epoxy Nanocomposites

8.1 Introduction

8.2 Optimization of the Curing Conditions

8.3 Fillers, Surface Modifications, and Ion Exchange

8.4 Nanocomposite Synthesis

8.5 Morphology

8.6 Barrier Properties

8.7 Effect of Excess Surface Modification Molecules

9 Unsaturated Polyester–Montmorillonite Nanocomposites by In-situ Polymerization

9.1 Introduction

9.2 Nanocomposites with MMT Introduced into UP Prepolymer or Resin

9.3 Nanocomposites with MMT Introduced during the Synthesis of Prepolymer

9.4 Conclusions

10 Polymer Clay Nanocomposites by In-situ Atom Transfer Radical Polymerization

11 Polybutadiene Clay Nanocomposites by In-situ Polymerization

11.1 Introduction

11.2 Generalities

11.3 Polybutadiene Nanocomposites

11.4 Conclusions and Perspectives

12 P3HT–MWNT Nanocomposites by In-situ Polymerization and Their Properties

12.1 Introduction

12.2 Multiwall CNTs

12.3 In-situ Synthesis of P3HT–MWNT Composites

12.4 The Properties and Characterization of P3HT–MWNT Nanocomposites

12.5 Conclusion and Outlook

13 Polystyrene–Montmorillonite Nanocomposites by In-situ Polymerization and Their Properties

13.1 Introduction

13.2 Morphology of Polymer–Clay Nanocomposites

13.3 Modification of MMT

13.4 In-situ Polymerization Methods

13.5 Properties of PS–MMT Nanocomposites Prepared via In-situ Techniques

13.6 Summary

14 Aliphatic Polyester and Poly(ester amide) Clay Nanocomposites by In-situ Polymerization

14.1 Introduction: Biodegradable Polymers and Their Nanocomposites

14.2 Aliphatic Polyester Clay Nanocomposites by In-situ Polymerization

14.3 PEAs Clay Nanocomposites by In-situ Polymerization

14.4 Conclusion

Acknowledgments

Index

Polymer Nano-, Micro- & Macrocomposites Series

Mittal, V. (ed.)

Surface Modification of Nanotube Fillers

Series: Polymer Nano-, Micro- and Macrocomposites (Volume 1)

2011

ISBN: 978-3-527-32878-9

Mittal, V. (ed.)

Characterization Techniques for Nanocomposites

Series: Polymer Nano-, Micro- and Macrocomposites (Volume 3)

2012

ISBN: 978-3-527-33148-2

Related Titles

Mittal, V. (ed.)

Optimization of Polymer Nanocomposite Properties

2010

ISBN: 978-3-527-32521-4

Mittal, V. (ed.)

Miniemulsion Polymerization Technology

2010

ISBN: 978-0-470-62596-5

Mittal, V. (ed.)

Polymer Nanotube Nanocomposites

Synthesis, Properties, and Applications

2010

ISBN: 978-0-470-62592-7

Matyjaszewski, K., Müller, A. H. E. (eds.)

Controlled and Living Polymerizations

From Mechanisms to Applications

2010

ISBN: 978-3-527-32492-7

Cosnier, S., Karyakin, A. (eds.)

Electropolymerization

Concepts, Materials and Applications

2010

ISBN: 978-3-527-32414-9

Leclerc, M., Morin, J.-F. (eds.)

Design and Synthesis of Conjugated Polymers

2010

ISBN: 978-3-527-32474-3

Pascault, J.-P., Williams, R. J. J. (eds.)

Epoxy Polymers

New Materials and Innovations

2010

ISBN: 978-3-527-32480-4

The Editor

Dr. Vikas Mittal

The Petroleum Institute

Chemical Engineering Department

Abu Dhabi

UAE

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© 2012 Wiley-VCH Verlag & Co. KGaA, Boschstr. 12, 69469 Weinheim, Germany

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Print ISBN: 978-3-527-32879-6

ePDF ISBN: 978-3-527-64012-6

oBook ISBN: 978-3-527-64010-2

ePub ISBN: 978-3-527-64011-9

ISSN: 2191-0421

Preface

In-situ intercalation method was reported by Toyota researchers for the synthesis of polyamide nanocomposites in the early nineties which led to the exponential growth in the nanocomposites research. For generation of polymer nanocomposites by this method, the layered silicate mineral was swollen in liquid monomer. After swelling, the polymerization of the monomer was initiated in the presence of filler. As monomer is present in and out of the filler interlayers, the generated structure is exfoliated or significantly intercalated. Since then, a large number of polymers like polyethylene, polypropylene (both cases have monomers as gases), PET, epoxy, polyurethane, and polystyrene have been synthesized in situ in the presence of filler to generate nanocomposites. In-situ intercalative polymerization in the presence of filler does provide distinct advantages as compared with other nanocomposite synthesis techniques like possibility to polymerize a large range of thermoplastic and thermosetting polymers, handling of gaseous or liquid monomers, handling of high-pressure polymerization, and easy control of heat of polymerization owing to dispersion medium present in the system. The current book also aims to highlight these advantages of in-situ polymerization in the light of generation of polymer nanocomposites with a large spectrum of polymer matrices.

Chapter 1 provides an overview on the various synthesis technologies of polymer nanocomposites and presents a wide spectrum of polymer nanocomposites prepared with in-situ intercalative polymerization. Chapter 2 reviews the polyamide nanocomposites synthesis by in-situ polymerization. PA6 and PA6,6 matrices and various in-situ synthesis methods to generate nanocomposites (like solution-melt polymerization technique, anhydrous-melt polymerization technique, direct solid-state polymerization technique, interfacial polycondesation technique) are discussed. Chapter 3 focuses on polyolefin nanocomposites generation. The effect of filler on the polymerization behavior and the polymer molecular structure is also analyzed. Chapter 4 describes the technique of gas phase-assisted polymerization for the generation of polymer nanocomposites. Composites with various fillers like clay, cellulose fibers, and carbon nanotubes are described. PET nanocomposites synthesized with in-situ polymerization are described in Chapter 5. Bio-based polymer nanocomposites by in-situ polymerization are discussed in Chapter 6 and control of filler-phase dispersion in the polymer matrix is reviewed. Chapter 7 describes synthesis and properties of thermoset polyurethane nanocomposites by in-situ polymerization, whereas another thermoset matrix of epoxy is discussed in Chapter 8 for the synthesis of polymer nanocomposites. Chapter 9 describes nanocomposites with unsaturated polyesters along with their properties. Chapter 10 reviews the use of controlled polymerization technique of atom transfer radical polymerization for the synthesis of polymer nanocomposites with in-situ polymerization. Polybutadiene-based polymer nanocomposites are discussed in Chapter 11 and synthesis and properties of P3HT nanocomposites with carbon nanotubes are detailed in Chapter 12. Chapter 13 describes one of the most common polymer polystyrene to synthesis nanocomposites with in-situ polymerization methods. Chapter 14 discusses clay-filled nanocomposites of aliphatic polyester and poly(esteramide) polymers.

It gives me immense pleasure to thank Wiley-VCH publishers for their kind support throughout the whole process. I dedicate this book to my mother and to my wife Preeti for being my constant sources of support and inspiration.

Vikas Mittal

List of Contributors

Yoshito Andou

Kyushu Institute of Technology

Eco-Town Collaborative R&D Center for the Environment and Recycling

2-4 Hibikino

Wakamatsu-ku, Kitakyushu-shi

Fukuoka 808-0196

Japan

Stuart A. Bateman

CSIRO

Materials Science and Engineering

Graham Road

Highett

VIC 3190

Australia

Anastasia C. Boussia

National Technical University of Athens

School of Chemical Engineering

Laboratory of Polymer Technology

Zographou Campus

15780 Athens

Greece

Dongyu Cai

Loughborough University

Department of Materials

Loughborough, LE11 3TU

UK

Feng Chen

Sichuan University

College of Polymer Science and Engineering

State Key Laboratory of Polymer Materials Engineering

Chengdu 610065

People’s Republic of China

Hua Deng

Sichuan University

College of Polymer Science and Engineering

State Key Laboratory of Polymer Materials Engineering

Chengdu 610065

People’s Republic of China

Takeshi Endo

Kinki University

Molecular Engineering Institute

11-6 Kayanomori

Iizuka, Fukuoka 820-8555

Japan

Lourdes Franco

Universitat Politècnica de Catalunya

Departament d’Enginyeria Química

Av. Diagonal 647

08028 Barcelona

Spain

Qiang Fu

Sichuan University

College of Polymer Science and Engineering

State Key Laboratory of Polymer Materials Engineering

Chengdu 610065

People’s Republic of China

Michal Kedzierski

Industrial Chemistry Research Institute

Department of Polyesters, Epoxide Resins and Polyurethanes

Rydygiera Street 8

01 793 Warsaw

Poland

Giuseppe Leone

CNR-ISMAC

Istituto per lo studio delle Macromolecole

via E. Bassini 5

20133 Milano

Italy

Zhongrui Li

University of Arkansas

Nanotechnology Center

Little Rock, AR 72204

USA

Abolfazl Maneshi

University of Waterloo

Department of Chemical Engineering

Waterloo, ON N2L 3G1

Canada

Vikas Mittal

The Petroleum Institute

Chemical Engineering Department

Abu Dhabi

UAE

Laura Morales-Gámez

Universitat Politècnica de Catalunya

Departament d’Enginyeria Química

Av. Diagonal 647

08028 Barcelona

Spain

Haruo Nishida

Kyushu Institute of Technology

Eco-Town Collaborative R&D Center for the Environment and Recycling

2-4 Hibikino

Wakamatsu-ku

Kitakyushu-shi, Fukuoka 808-0196

Japan

Grady A. Nunnery

Georgia Institute of Technology

School of Materials Science and Engineering

Atlanta, GA 30332

USA

Constantine D. Papaspyrides

National Technical University of Athens

School of Chemical Engineering, Laboratory of Polymer Technology, Zographou Campus

15780 Athens

Greece

Lawrence A. Pranger

Georgia Institute of Technology

School of Materials Science and Engineering

Atlanta, GA 30332

USA

Jordi Puiggalí

Universitat Politècnica de Catalunya

Departament d’Enginyeria Química

Av. Diagonal 647

08028 Barcelona

Spain

Greg G. Qiao

University of Melbourne

Department of Chemical and Bimolecular Engineering

Polymer Science Group

Parkville

VIC 3010

Australia

Giovanni Ricci

CNR-ISMAC

Istituto per lo studio delle Macromolecole

via E. Bassini 5

20133 Milano

Italy

Alfonso Rodríguez-Galán

Universitat Politècnica de Catalunya

Departament d’Enginyeria Química

Av. Diagonal 647

08028 Barcelona

Spain

Leonardo Simon

University of Waterloo

Department of Chemical Engineering

Waterloo, ON N2L 3G1

Canada

Ranya Simons

University of Melbourne

Department of Chemical and Bimolecular Engineering

Polymer Science Group

Parkville

VIC 3010

Australia

and

CSIRO

Materials Science and Engineering

Graham Road

Highett

VIC 3190

Australia

João Soares

University of Waterloo

Department of Chemical Engineering

Waterloo, ON N2L 3G1

Canada

Mo Song

Loughborough University

Department of Materials

Loughborough, LE11 3TU

UK

Rina Tannenbaum

Georgia Institute of Technology

School of Materials Science and Engineering

Atlanta, GA 30332

USA

Stamatina N. Vouyiouka

National Technical University of Athens

School of Chemical Engineering

Laboratory of Polymer Technology

Zographou Campus

15780 Athens

Greece

Ke Wang

Sichuan University

College of Polymer Science and Engineering

State Key Laboratory of Polymer Materials Engineering

Chengdu 610065

People’s Republic of China

Qin Zhang

Sichuan University

College of Polymer Science and Engineering

State Key Laboratory of Polymer Materials Engineering

Chengdu 610065

People’s Republic of China

Hanying Zhao

Nankai University

Department of Chemistry

Tianjin 300071

China

Liqiu Zheng

University of Arkansas

Nanotechnology Center

Little Rock, AR 72204

USA

1

In-situ Synthesis of Polymer Nanocomposites

Vikas Mittal

1.1 Introduction

It was the pioneering work of Toyota researchers toward the development of polymeric nanocomposites in the early 90s [1, 2], in which electrostatically held 1-nm-thick layers of the layered aluminosilicates were dispersed in the polyamide matrix on a nanometer level, which led to an exponential growth in the research in these layered silicate nanocomposites. These nanocomposites were based on the in-situ synthesis approach in which monomer or monomer solution was used to swell the filler interlayers followed by polymerization. Subsequently, Giannelis and coworkers [3, 4] also reported the route of melt intercalation for the synthesis of polymer nanocomposites.

Montmorillonite has been the most commonly used layered aluminosilicate in most of the studies on polymer nanocomposites. The general formula of montmorillonites is Mx(Al4−xMgx)Si8O20(OH)4 [5, 6]. Its particles consist of stacks of 1-nm-thick aluminosilicate layers (or platelets) with a regular gap in between (interlayer). Each layer consists of a central Al-octahedral sheet fused to two tetrahedral silicon sheets. In the tetrahedral sheets, silicon is surrounded by four oxygen atoms, whereas in the octahedral sheets, aluminum atom is surrounded by eight oxygen atoms. Isomorphic substitutions of aluminum by magnesium in the octahedral sheet generate negative charges, which are compensated for by alkaline-earth- or hydrated alkali-metal cations. Owing to the low charge density (0.25–0.5 equiv. mol−1) of montmorillonites, a larger area per cation is available on the surface that leads to a lower interlayer spacing in the modified montmorillonite after surface ion exchange with alkyl ammonium ions. On the contrary, the minerals with high charge density (1 equiv. mol−1) like mica have much smaller area per cation and can lead to much higher basal plane spacing after surface modification; however, owing to very strong electrostatic forces present in the interlayers due to the increased number of ions, these minerals do not swell in water and thus do not allow the cation exchange. In contrast, aluminosilicates with medium charge densities of 0.5–0.8 equiv. mol−1 like vermiculite offer a potential of partial swelling in water and cation exchange that can lead to much higher basal plane spacing in the modified mineral if optimum ion exchange is achieved. Vaia et al. [7] also proposed further insight into the positioning of the surface modification molecules on the surface of the filler based on FTIR experiments. By monitoring frequency shifts of the asymmetric CH2 stretching and bending vibrations, they found that the intercalated chains exist in states with varying degrees of order. In general, as the interlayer packing density or the chain length decreases (or the temperature increases), the intercalated chains adopt a more disordered, liquid-like structure resulting from an increase in the gauche/trans conformer ratio.

Nanocomposites with a large number of polymer matrices have been synthesized and significant enhancements in the composite properties have been reported. The improvement in the mechanical properties of the nanocomposites is generally reported, though a synergistic enhancement in the other composite properties like gas barrier resistance is also generally achieved. Figure 1.1a demonstrates the decrease in oxygen permeation through the polyurethane, epoxy, and polypropylene nanocomposites as a function of inorganic filler volume fraction [8–10]. Figure 1.1b also shows the improvement in mechanical properties of the polypropylene and polyethylene nanocomposites as a function of filler volume fraction [11–13]. The polypropylene composites have been generated by using two different filler surface modifications containing ammonium and imidazolium ions. The microstructure of the nanocomposites is also ideally classified as unintercalated (phase separated), intercalated, and exfoliated composites. The composite microstructure is classified as exfoliated when the filler platelets are completely delaminated into their primary nanometer scale size and the platelets are far apart from each other so that the periodicity of this platelet arrangement is totally lost. When a single or sometimes more than one extended polymer chain is intercalated into the clay interlayers, but the periodicity of the clay platelets is still intact, such a microstructure is termed as intercalated. On the basis of the interfacial interactions and mode of mixing of the organic and inorganic phases, it is possible that both the phases do not intermix at all and a microcomposite or unintercalated composite is formed. Transmission electron microscopy (TEM) and X-ray diffraction (XRD) are the most commonly used methods to characterize the microstructure of the nanocomposites. Figure shows the TEM micrographs depicting the various idealized morphologies of the polymer nanocomposite structures [15]. However, it should be noticed that these classifications of the composite microstructure as exfoliated and intercalated are not very realistic as generally in reality a mixture of different morphologies is present. Figure also shows the three idealized morphologies of immiscible, intercalated, and exfoliated composites [16]. The presence or absence of diffraction peaks in the XRD of the composites is used to assess information about the microstructure of the composites. The intensity of the X-ray diffractograms is generally taken as a measure to classify the microstructure as intercalated or exfoliated. However, it should be noticed that the X-ray signal are very qualitative in nature and are strongly influenced by the sample preparation, orientation of the platelets, as well as defects present in the crystal structure of the montmorillonites. Therefore, the classification of the nanocomposite microstructure just based on the intensity can be faulty. Also, the presence of diffraction signal in the diffractograms of the composite does not mean that 100% of the microstructure is intercalated and it is quite possible to have significant amount of exfoliation present in the composite. Similarly, absence of diffraction signal also does not guarantee the complete exfoliation as small or randomly oriented intercalated platelets may still be present in the composite.