Handbook of Metathesis, Volume 3 E-Book

• Herausgeber: Wiley-VCH
• Kategorie: Wissenschaft und neue Technologien
• Sprache: Englisch

Seitenzahl: 686

Veröffentlichungsjahr: 2015

Beschreibung

The second edition of the "go-to" reference in this field is completely updated and features more than 80% new content, with emphasis on new developments in the field, especially in industrial applications. No other book covers the topic in such a comprehensive manner and in such high quality.

Edited by the Nobel laureate R. H. Grubbs and E. Khosravi, Volume 3 of the 3-volume work focusses on polymer synthesis. With a list of contributors that reads like a "Who's-Who" of metathesis, this is an indispensable one-stop reference for chemists in academia and industry.

View the set here - http://www.wiley.com/WileyCDA/WileyTitle/productCd-3527334246.html

Other available volumes:

Volume 1: Catalyst Development and Mechanism, Editors: R. H. Grubbs and A. G. Wenzel - http://www.wiley.com/WileyCDA/WileyTitle/productCd-3527339485.html

Volume 2: Applications in Organic Synthesis, Editors: R. H. Grubbs and D. J. O´Leary - http://www.wiley.com/WileyCDA/WileyTitle/productCd-3527339493.html

Leseprobe

Table of Contents

Cover

Title Page

Copyright

Preface

List of Contributors

Chapter 1: Synthesis of Homopolymers and Copolymers

1.1 Introduction

1.2 Initiators

1.3 Monomers

1.4 Synthesis of Polymers with Complex Architectures

1.5 Stereochemistry and Sequence Control in ROMP

1.6 Conclusion

References

Chapter 2: ROMP in Dispersed Media

2.1 Introduction

2.2 Emulsion ROMP

2.3 Dispersion ROMP

2.4 Suspension ROMP

2.5 Formation of Nanoparticles

2.6 Conclusion

References

Chapter 3: Telechelic Polymers

3.1 Introduction

3.2 Mono-telechelic Polymers

3.3 Homo-telechelic Polymers

3.4 Hetero-telechelic Polymers

3.5 Conclusions and Outlook

Acknowledgments

References

Chapter 4: Supramolecular Polymers

4.1 Introduction

4.2 Main-Chain Supramolecular Polymers

4.3 Side-Chain-Functionalized Supramolecular Polymers

4.4 Supramolecular Architectures by Design

4.5 Conclusion

References

Chapter 5: Synthesis of Materials with Nanostructured Periodicity

5.1 Introduction

5.2 Sequential ROMP

5.3 Inorganic Composite Materials

5.4 ABA Triblock Copolymers

5.5 Nanostructures with Domain Sizes Exceeding 100 nm

5.6 Conclusions

References

Chapter 6: Synthesis of Nanoparticles

6.1 Introduction

6.2 Formation of Nanoparticles

6.3 Synthesis via Grafting-through Approach

6.4 Synthesis via Grafting-to Approach

6.5 Synthesis via Grafting-from Approach

6.6 Summary

References

Chapter 7: Synthesis of Biodegradable Copolymers

7.1 Introduction

7.2 Polyester-Functionalized Polymers

7.3 Peptide-Functionalized Polymers

7.4 Carbohydrate-Functionalized Polymers

7.5 Antimicrobial Polymers

7.6 Polymeric Betaines

7.7 ROMP Polymers as Drug Carriers

7.8 ROMP Polymers for Tissue Scaffolds

7.9 Conclusion

References

Chapter 8: Biologically Active Polymers

8.1 Introduction

8.2 Benefits of ROMP for Bioactive Polymer Synthesis

8.3 Biologically Active Polymeric Displays

8.4 Exploiting the Bulk Properties of Polymers

8.5 Probes of Biological Processes

8.6 Outlook

References

Chapter 9: Combination of Olefin Metathesis Polymerization with Click Chemistry

9.1 Introduction

9.2 Attaching Functional Groups for Click Reaction

9.3 Copper-Catalyzed Azide/Alkyne Click Reaction

9.4 Diels–Alder Click Reaction

9.5 Thiol–Ene Reaction

9.6 Thiol-Michael Addition

9.7 Meldrum's Acid-Containing Polymers as Precursor for Ketene Coupling

9.8 Nitrile Oxide Cycloaddition

Acknowledgment

References

Chapter 10: Self-Healing Polymers

10.1 Introduction

10.2 Monomer Storage

10.3 Catalyst Stability and Protection

10.4 Catalyst and Monomer Choice

10.5 Intrinsic Self-Healing Polymers

10.6 Conclusions

References

Chapter 11: Functional Supports and Materials

11.1 Introduction

11.2 Preparation of Functional Supports

11.3 Functional Monolithic Supports

11.4 Twenty-First Century Functional Supports

11.5 Summary and Outlook

Acknowledgment

References

Chapter 12: Latent Ruthenium Catalysts for Ring Opening Metathesis Polymerization (ROMP)

12.1 Introduction

12.2 Thermal Activation

12.3 Light-Induced Activation

12.4 Chemical Activation

12.5 Mechanical Activation

12.6 Conclusions

References

Chapter 13: ADMET Polymerization

13.1 Introduction

13.2 ADMET: The Metathesis Polycondensation Reaction

13.3 ADMET of Nonconjugated Hydrocarbon Dienes

13.4 ADMET Copolymerization

13.5 ADMET of Functionalized Dienes

13.6 Functional Materials

13.7 Modeling Polyethylene

13.8 Conjugated Polymers

13.9 Solid-State Polymerization

13.10 ADMET Depolymerization

13.11 Telechelic Oligomers

13.12 Complex Polymer Architectures

13.13 Biorenewable Polymers

13.14 Conclusions and Outlook

References

Chapter 14: Biorenewable Polymers

14.1 Introduction

14.2 ADMET

14.3 ROMP

14.4 Conclusion

References

Chapter 15: Polymerization of Substituted Acetylenes

15.1 Introduction

15.2 Polymerization Reactions

15.3 Catalysts

15.4 Recent Catalysts for Living Polymerization

15.5 Polymerization of Monosubstituted Acetylenes

15.6 Polymerization of Disubstituted Acetylenes

15.7 Polymer Modification Reactions

15.8 Properties of Polymers

References

Index

End User License Agreement

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Guide

Cover

Table of Contents

Preface

Begin Reading

List of Illustrations

Figure 1.1

Figure 1.2

Figure 1.3

Figure 1.4

Figure 1.5

Figure 1.6

Figure 1.7

Figure 1.8

Figure 1.9

Figure 1.10

Figure 1.11

Figure 1.12

Figure 1.13

Figure 1.14

Figure 1.15

Scheme 2.1

Scheme 2.2

Scheme 2.3

Scheme 2.4

Scheme 2.5

Scheme 2.6

Scheme 2.7

Scheme 2.8

Scheme 2.9

Scheme 2.10

Scheme 2.11

Scheme 2.12

Figure 3.1

Figure 3.2

Figure 3.3

Figure 3.4

Figure 3.5

Figure 3.6

Figure 3.7

Figure 3.8

Figure 3.9

Figure 3.10

Figure 3.11

Figure 3.12

Figure 3.13

Figure 3.14

Figure 3.15

Figure 4.1

Figure 4.2

Figure 4.3

Figure 4.4

Figure 4.5

Figure 4.6

Figure 4.7

Figure 4.8

Figure 4.9

Figure 4.10

Figure 4.11

Figure 4.12

Figure 4.13

Figure 4.14

Figure 5.1

Figure 5.2

Figure 5.3

Figure 5.4

Figure 5.5

Figure 5.6

Figure 5.7

Figure 5.8

Figure 5.9

Figure 5.10

Figure 5.11

Figure 5.15

Figure 5.13

Figure 5.14

Figure 5.16

Figure 6.1

Figure 6.2

Figure 6.3

Figure 6.4

Figure 6.5

Figure 6.6

Figure 6.7

Figure 6.8

Figure 6.9

Figure 6.10

Figure 6.11

Figure 6.12

Figure 6.13

Figure 6.14

Figure 6.15

Figure 6.16

Figure 6.17

Figure 6.18

Figure 6.19

Figure 6.20

Figure 6.21

Figure 6.22

Figure 6.23

Figure 6.24

Figure 6.25

Figure 6.26

Figure 6.27

Figure 6.28

Figure 6.29

Figure 6.30

Figure 6.31

Figure 7.1

Figure 7.2

Figure 7.3

Figure 7.4

Figure 7.5

Figure 7.6

Figure 7.7

Figure 7.8

Figure 7.9

Figure 7.10

Figure 7.11

Figure 8.1

Figure 8.2

Figure 8.3

Figure 8.4

Figure 8.5

Figure 8.6

Figure 8.7

Figure 8.8

Figure 8.9

Figure 8.10

Figure 8.11

Figure 8.12

Figure 8.13

Figure 8.14

Figure 8.15

Figure 8.16

Figure 8.17

Figure 8.18

Figure 8.19

Figure 8.20

Figure 8.21

Figure 8.22

Figure 8.23

Scheme 9.1

Scheme 9.2

Scheme 9.3

Scheme 9.4

Scheme 9.5

Scheme 9.6

Scheme 9.7

Scheme 9.8

Scheme 9.9

Scheme 9.10

Scheme 9.11

Scheme 9.12

Figure 10.1

Figure 10.2

Figure 10.3

Figure 10.4

Figure 10.5

Figure 10.6

Figure 10.7

Figure 10.8

Figure 10.9

Scheme 11.1

Scheme 11.2

Scheme 11.3

Scheme 11.4

Scheme 11.5

Scheme 11.6

Scheme 11.7

Scheme 11.8

Scheme 11.9

Scheme 11.10

Scheme 11.11

Scheme 11.12

Scheme 11.13

Scheme 11.14

Figure 12.1

Figure 12.2

Figure 12.3

Scheme 12.1

Figure 12.4

Figure 12.5

Scheme 12.2

Figure 12.6

Scheme 12.3

Figure 12.7

Figure 12.8

Figure 12.9

Figure 12.10

Figure 12.11

Figure 12.12

Figure 12.13

Figure 12.14

Figure 12.15

Figure 12.16

Figure 12.17

Figure 12.18

Scheme 12.4

Figure 12.19

Scheme 12.5

Scheme 12.6

Scheme 12.7

Figure 12.20

Scheme 12.8

Figure 12.21

Scheme 12.9

Scheme 12.10

Scheme 12.11

Scheme 12.12

Figure 12.13

Scheme 12.14

Scheme 12.15

Figure 12.22

Scheme 12.16

Figure 12.23

Figure 13.1

Figure 13.2

Figure 13.3

Figure 13.4

Figure 13.5

Figure 13.6

Figure 13.7

Figure 13.8

Figure 13.9

Figure 13.10

Figure 13.11

Figure 13.12

Figure 13.13

Figure 13.14

Figure 13.15

Figure 13.16

Figure 13.17

Figure 13.18

Figure 13.19

Figure 13.20

Figure 13.21

Figure 13.22

Figure 13.23

Figure 13.24

Figure 13.25

Figure 13.26

Figure 14.1

Figure 14.2

Figure 14.3

Figure 14.4

Figure 14.5

Figure 14.6

Figure 14.7

Figure 14.8

Figure 14.9

Figure 14.10

Figure 14.11

Figure 14.12

Figure 14.13

Figure 14.14

Scheme 15.1

Scheme 15.2

Figure 15.1

Scheme 15.3

List of Tables

Table 9.1

Table 9.2

Table 10.1

Table 10.2

Table 10.3

Table 10.4

Table 11.1

Table 14.1

Table 14.2

Table 14.3

Table 15.1

Table 15.2

Table 15.3

Edited by Robert H. Grubbs and Ezat Khosravi

Handbook of Metathesis

Volume 3: Polymer Synthesis

Second Edition

Editors

Prof. Dr. Robert H. Grubbs

California Institute of Technology

Division of Chemistry and Chemical Engineering

E. California Blvd 1200

Pasadena, CA 91125

United States

Dr. Ezat Khosravi

University of Durham

Dept. of Chemistry

South Road

Durham DH1 3LE

United Kingdom

Handbook of Metathesis

Second Edition

Set ISBN (3 Volumes): 978-3-527-33424-7

oBook ISBN: 978-3-527-67410-7

Vol 1: Catalyst Development and Mechanism, Editors: R. H. Grubbs and A. G. Wenzel ISBN: 978-3-527-33948-8

Vol 2: Applications in Organic Synthesis, Editors: R. H. Grubbs and D. J. O'Leary ISBN: 978-3-527-33949-5

All books published by Wiley-VCH are carefully produced. Nevertheless, authors, editors, and publisher do not warrant the information contained in these books, including this book, to be free of errors. Readers are advised to keep in mind that statements, data, illustrations, procedural details or other items may inadvertently be inaccurate.

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Preface

In 2003, the first edition of the Handbook of Metathesis comprehensively covered the origins of the olefin metathesis reaction and the myriad of applications blossoming from the development of robust, homogeneous transition-metal catalysts. In the intervening 10 years, applications and advances in this field have continued to exponentially increase. To date, 3732 publications regarding olefin metathesis have been reported; of these, 2292 have been reported since 2003! 1 By 2005, olefin metathesis had become so integral to the field of organic synthesis that the Nobel Prize in Chemistry was awarded to the field (Yves Chauvin, Robert H. Grubbs, and Richard R. Schrock) [1, 2].

In light of these many advancements, a second edition of the Handbook is quite timely. Early on in the planning, it was decided that rather than simply updating the 2003 edition, the second edition would instead emphasize important advancements (e.g., new ligands, diastereoselective metathesis, alkyne metathesis, industrial applications, self-healing polymers) that have occurred during the past decade. In addition, the past 10 years have seen important developments in our understanding of the metathesis mechanism utilizing both computational and mechanistic studies. A greater knowledge of catalyst decomposition, product purification, and the use of supported catalysts and nontraditional reaction media have further enhanced the utility of metathesis systems. A number of new applications are now becoming commercialized based on these new catalyst systems. For example, the first pharmaceutical that uses olefin metathesis in a key step is now commercially available, and a biorefinery that utilizes a homogeneous catalyst is now in production.

Similar to the first edition of this Handbook, contributions have been arranged into three volumes. Volume I (Anna Wenzel, coeditor) emphasizes recent catalyst developments and mechanism and is intended to provide a foundation for the applications discussed throughout the rest of the Handbook. Volume II (Dan O'Leary, coeditor) covers synthetic applications of the olefin metathesis reaction, and polymer chemistry is the topic of Volume III (Ezat Khosravi, coeditor). Chapter topics have been selected to provide comprehensive coverage of these areas of olefin metathesis. Contributors, many of whom are pioneers in the field, were chosen based on their firsthand experience with the topics discussed.

We wish to sincerely thank all the contributors for their diligence in writing and editing their chapters. Our goal was to comprehensively cover the complete breadth of the olefin metathesis reaction – this Handbook would not have been possible without all their time and effort! It was truly a pleasure and an honor to work with everyone!

Claremont, CA

Durham, UK

Pasadena, CA

Anna G. Wenzel, Daniel J. O'Leary

Ezat Khosravi, and

Robert H. Grubbs

November 20th, 2014

1

 Data obtained from keyword searches conducted within the ISI Web of Science (accessed 1/18/2014).

References

1. Nobel Prizes.org Development of the Metathesis Method in Organic Synthesis,

http://www.nobelprize.org/nobel_prizes/chemistry/laureates/2005/advanced-chemistryprize2005.pdf

(accessed 18 January 2014).

2. Rouhi, M. (2005)

Chem. Eng. News

,

83

, 8.

List of Contributors

Emily B. Anderson

Universität Stuttgart

Institut fär Polymerchemie

Makromolekulare Stoffe und Faserchemie

Pfaffenwaldring 55

70550 Stuttgart

Germany

Wolfgang H. Binder

Martin-Luther University Halle-Wittenberg

Faculty of Sciences II

Chair of Macromolecular Chemistry

von Danckelmannplatz 4

06120 Halle (Saale)

Germany

Martin-Luther-Universität

Insitut fär Chemie

Von-Danckelmann-Platz 4

06120 Halle

Germany

Dylan J. Boday

IBM Materials Engineering

1130/9032

9000 S. Rita Road

Tucson, AZ 85744

USA

Michael R. Buchmeiser

Universität Stuttgart

Institut fär Polymerchemie

Makromolekulare Stoffe und Faserchemie

Pfaffenwaldring 55

70550 Stuttgart

Germany

Abraham Chemtob

Université de Haute Alsace

Laboratoire de Photochimie et d'Ingénierie Macromoléculaire

3 rue Alfred Werner

68093 Mullhouse

France

Izabela Czelusniak

University of Wroclaw

Faculty of Chemistry

14 F. Joliot-Curie

50-383 Wroclaw

Poland

Elizabeth Elacqua

New York University

Molecular Design Institute

100 Washington Square East

New York, NY 10003-6688

USA

Joshua M. Fishman

University of Wisconsin

Department of Chemistry

1101 Wisconsin Avenue

Madison, WI 53706

USA

Nathan C. Gianneschi

University of California

Department of Chemistry and Biochemistry

9500 Gilman Drive

San Diego, CA 92093

USA

Robert H. Grubbs

California Institute of Technology

Division of Chemistry and Chemical Engineering

1200

E. California Blvd.

Pasadena, CA 91125

USA

Nils Hanik

University of Fribourg

Chemistry Department

Chemin du Musee 9

1700 Fribourg

Switzerland

Valérie Héroguez

CNRS UMR5629

Laboratoire de Chimie des Polymères Organiques

16 avenue Pey-Berland

F33600 Pessac

France

Carrie R. James

University of California

Department of Chemistry and Biochemistry

9500 Gilman Drive

San Diego, CA 92093

USA

Ezat Khosravi

University of Durham

Dept. of Chemistry

South Road

Durham DH1 3LE

United Kingdom

Laura L. Kiessling

University of Wisconsin

Department of Chemistry

1101 Wisconsin Avenue

Madison, WI 53706

USA

Andreas F.M. Kilbinger

University of Fribourg

Chemistry Department

Chemin du Musee 9

1700 Fribourg

Switzerland

Steffen Kurzhals

Martin-Luther University Halle-Wittenberg

Faculty of Sciences II

Chair of Macromolecular Chemistry

von Danckelmannplatz 4

06120 Halle (Saale)

Germany

Martin-Luther-Universität

Insitut fär Chemie

Von-Danckelmann-Platz 4

06120 Halle

Germany

Gabriel Lemcoff

Ben-Gurion University

Department of Chemistry

84105 Beer-Sheva

Israel

Toshio Masuda

Shanghai University

Department of Polymer Materials

Shangda Street 99

Mailbox 152

Shanghai 200444

China

Timothy C. Mauldin

IBM Materials Engineering

1130/9032

9000 S. Rita Road

Tucson, AZ 85744

USA

Garret M. Miyake

California Institute of Technology

Division of Chemistry and Chemical Engineering

1200 E. California Blvd.

Pasadena, CA 91125

USA

John H. Phillips

Materia Inc

60 N. San Gabriel Blvd

Pasadena, CA 91107

USA

Damien Quemener

UM2 UMR5635

Institut Europèen des Membranes

2 place E. Bataillon

34095 Montpellier

France

Anthony M. Rush

University of California

Department of Chemistry and Biochemistry

9500 Gilman Drive

San Diego, CA 92093

USA

Michael D. Schulz

University of Florida

Center for Macromolecular Science and Engineering

Department of Chemistry

318 Leigh Hall

Gainesville, Florida 32611

USA

Christian Slugovc

Graz University of Technology

Institute of Chemistry and Technology of Materials (ICTM)

NAWI Graz

Stremayrgasse 9

8010 Graz

Austria

TU Graz

ICTOS

Stremayrgasse 16/1

8010 Graz

Niels ten Brummelhuis

New York University

Molecular Design Institute

100 Washington Square East

New York, NY 10003-6688

USA

Eyal Tzur

Ben-Gurion University

Department of Chemistry

84105 Beer-Sheva

Israel

Kenneth B. Wagener

University of Florida

Center for Macromolecular Science and Engineering

Department of Chemistry

318 Leigh Hall

Gainesville, Florida 32611

USA

Marcus Weck

New York University

Molecular Design Institute

100 Washington Square East

New York, NY 10003-6688

USA

Raymond A. Weitekamp

California Institute of Technology

Division of Chemistry and Chemical Engineering

1200 E. California Blvd.

Pasadena, CA 91125

USA

Afang Zhang

Shanghai University

Department of Polymer Materials

Shangda Street 99

Mailbox 152

Shanghai 200444

China

1Synthesis of Homopolymers and Copolymers

Christian Slugovc

1.1 Introduction

Ring-opening metathesis polymerization (ROMP) is a versatile chain-growth polymerization technique in which mono or polycyclic olefins undergo ring opening, thereby forming a linear polymer chain. ROMP is typically initiated by group VI or VIII carbene complexes and is capable of forming functionally diverse polymers. Depending on the use of a proper initiator and monomer used, the polymerization is controlled and living, allowing for the precise preparation of diverse polymer architectures with narrow molecular weight distributions. Especially with ruthenium-based initiators, the scope of ROMP is further extended, as most functional groups are tolerated and exclusion of moisture or air is not necessary. These characteristics make ROMP initiated by ruthenium complexes a competitive alternative to living radical polymerization methods. As a consequence, research on ROMP in the last 10 years has been focused on obtaining precision and diversity of macromolecular architectures bearing diverse functionalities. Mostly, ruthenium-based initiators have been used because of their paramount functional group tolerance. Only recently have molybdenum-based initiators staged a comeback because of their ability to provide stereoselective ROMP.

The basic mechanism of ROMP is shown in Figure 1.1. In the initiation step, a metal carbene species undergoes olefin metathesis with the monomer being, in most cases, a strained cyclic olefin. The newly formed carbene complex then performs repeated insertions of the monomer in the propagation step. The initiation rate constant ki should be significantly larger than kp in order to obtain controlled polymerization, that is, every initiator makes a polymer chain. Undesired termination should not occur. The intended termination, upon addition of a proper reactant, leads to the cleaving off and deactivation of the active site and to the introduction of an end group to the polymer chain. Furthermore, undesired side reactions, known as back biting, may occur depending on the nature of the initiator used. In this process, the carbene moiety at a growing polymer chain might react with a double bond from another polymer chain or from its own polymer chain, leading to chain transfer reactions that are detrimental for obtaining polymers with narrow molecular weight distributions and the synthesis of precision polymers.

Figure 1.1 Basic ROMP mechanism.

This chapter focuses on recent development in the synthesis of homo and copolymers via ROMP. Since 2003, several book chapters and review articles covering this field or aspects of this field have been published [1–13]. Therefore, this chapter is not aimed to be a comprehensive review, but rather a concise overview of influential work conducted in the last decade.

1.2 Initiators

Most of the work published involving ROMP is performed using a handful of commercially available ruthenium-based initiators (Figure 1.2). Grubbs first- (G1) and second- (G2) generation ruthenium initiators were state of the art when the first edition of the Handbook of Metathesis was published. Shortly afterward, the high potential of pyridine-containing species (sometimes referred to as Grubbs third-generation ruthenium initiators (G3)) in ROMP was recognized [14, 15]. Nowadays, G3 and its indenylidene analog M31 [16] are the two most often used ruthenium initiators capable of providing controlled living polymerization.

Figure 1.2 Most commonly used initiators for ROMP.

G1 provides, in the case of many monomers, controlled living polymerization [17, 18] but its functional group tolerance is somewhat lower [19] than that of G2, G3, or M31. On the other hand, G2 is more active and provides fast polymerization because of the presence of the N-heterocyclic carbene ligand but does not provide controlled polymerization [20]. In this case, the initiation rate constant (ki) is lower than the propagation rate constant (kp), resulting in a low initiation efficacy and polymers with high molecular weight and broad molecular weight distribution [21]. Nevertheless, both initiators G1 and G2 are still in use for the preparation of polymers even today. The pyridine-bearing initiators G3 and M31 initiate very rapidly [15] and propagate fast (). They provide controlled polymerization and are therefore suitable for the preparation of block copolymers [16, 22, 23]. The initiator G3 bearing 3-bromopyridine as the ligand initiates the fastest; however, it is not particularly stable, so G3 with unsubstituted pyridine ligands is nowadays commonly used.

Other ruthenium initiators have also been used for ROMP, mostly designed to meet special requirements (Figure 1.3). Complexes 1 and 2 have been used as water-soluble ruthenium initiators [24, 25]. Complex 3 was aimed at fluorescence marking of ROMP polymers [26]. Complex 4, bearing a fluorinated phosphine ligand, has been used to demonstrate the feasibility of phase transfer activation in ROMP [27]. Complexes 5 and 6 are examples for initiators that can be activated upon irradiation with UV light. Complex 5 needs a tandem approach for its activation, that is, it must be used in combination with a photo acid generator [28]. Complex 6 is a commercially available example of an UV-activated initiator for ROMP [29, 30]. Activation of latent initiators upon a proper stimulus is an important research branch in ROMP. Other triggers such as UV irradiation, mechanical force [31], addition of acids [32] or anions [33], and higher temperature [32, 34] have also been investigated.

Figure 1.3 Ruthenium initiators designed for special applications (Mes = mesityl).

Complex 7 (Figure 1.4), initially synthesized by Förstner [35], was recognized by Grubbs [36] to provide cyclic polymers, which is very interesting, as their synthesis is hard to accomplish with conventional polymerization methods. Upon addition of the monomer, this initiator produces a polymer chain, which remains attached to the initiator at both ends (Figure 1.4). This intended situation leads eventually to intramolecular chain transfer via olefin metathesis, back biting, and with the growing polymer chain releasing the cyclic polyolefin and the initiator 7. This process was termed ring expansion metathesis polymerization (REMP) [36, 37]. The use of REMP allowed the preparation of cyclic polyethylene (PE) from cyclooctene (COE) (8) and subsequent hydrogenation of the resulting polymer [36]. Minor variations of the structure of the initiator, that is, varying the lengths of the tether, led to major effects on the kinetics of the polymerization. A tether length of 6 or longer provides rapid molecular weight growth, while tether lengths smaller than 6 gives competitive rates of propagation and initiator release. These tether length levels are valid for initiators bearing unsaturated NHC ligands, and a saturated NHC ligand generally leads to a higher activity at a given tether length [38, 39].

Figure 1.4 Mechanism of REMP and the monomers used.

Most work on REMP was done with COE (8) or cyclooctadiene (COD) (9) but functionalized monomers can also be used. A dendronized macro-monomer 10 (Figure 1.4) has been used under REMP conditions, leading to the formation of cyclic nanostructures with a diameter of 35–40 nm [40]. Recently, a REMP-derived cyclic macro-initiator derived from monomer 11 was used to prepare cyclic brush copolymers by combining REMP with triazabicyclodecene-catalyzed ring-opening polymerization of a cyclic ester [41]. Furthermore, REMP processes were developed for the synthesis of functional cyclic polymers, cyclic polymer brushes, and cyclic gels [42, 43].

1.3 Monomers

The most commonly used monomer for ROMP is norbornene (NBE) and its derivatives because their high degree of ring strain affords rapid polymerization. Most importantly, a whole family of NBE derivatives are easily accessible via the Diels–Alder reaction of cyclopentadiene (CPD) or furan and an olefin, for example, readily commercially available acrylates. Some challenges in controlled living polymerization arise because of the fact that endo-substituted NBEs polymerize much slower than their exo-substituted counterparts. In some cases, preferably diastereo-pure monomers have to be used, for example, ROMP of monomers 12 and 13 using G2 (Figure 1.5) [44–46].

Figure 1.5 Amino acid-functionalized monomers (12, 13), reactivity of disubstituted NBE derivatives (disubstituted NBE model), active ester-bearing NBE for post-polymerization functionalization (14), isoxazolino NBE derivative (15), NBE with functional unit for cell adhesion (16).

An NBE-based monomer is composed of the polymerizable group (the strained bicyclic moiety) and a functional unit (F) that is attached via an anchor group (A), in many cases via a spacer (S) (Figure 1.5). The anchor group, in addition to providing a synthetically feasible connection to functional unit, also influences the reactivity of the monomer during propagation [47, 48]. Furthermore, substitution of the norbornene with anchor groups is decreasing the probability of the occurrence of chain transfer reactions.

The attachment of a functional unit to the polymer chain can be done before polymerization of the monomer but also in a post-polymerization functionalization approach by preparing activated polymers with monomers such as 14 [49–53]. The NBE derivative containing isoxazolino anchor group 15, which is employed in linking the functional unit to the polymerizable group, was polymerized with G1, G2, and the Schrock's initiator Mo(CHCMe2Ph)(N-2,6-iPr2C6H3)(OtBu)2 to produce polymers containing a sugar [54]. Monomer 16 containing the synthetically demanding tripeptide motif linked to NBE via an amide group has been subjected to ROMP to obtain polymers to serve as inhibitors of fibroblast adhesion [55].

Cyclobutene (CBE) derivatives have higher ring strain than NBE and they are a valuable addition to the monomer toolbox for ROMP. ROMP of 3,4-disubstituted CBEs yield polymers with a high density of functional groups and a strictly linear 1,4-linked polybutadiene (PBD) backbone, which is not accessible with other polymerization methods. CBE monomer 17 bearing cis-3,4-substituents is more reactive than the trans isomer 18 (Figure 1.6) [56]. The monomer 19 has been used for the combination of ROMP and ATRP [57, 58].

Figure 1.6 CBE-based monomers.

Cyclobutene-1-carboxamide 20 was polymerized with G3, yielding regio and stereoselective functionalized polymers [59]. The polymerization is approximately four times slower than in case of 3,4-disubstituted CBEs. CBE-carbinol esters 21 were also polymerized with G3 but the regio and stereochemistry could not be controlled [60]. Interestingly, ROMP of 1-cycobutene carboxylic acid esters 22 and tertiary amide derivatives 23 did not result in the formation of polymers because of an electronic and a steric effect, respectively.

ROMP of COE is not as facile as CBE or NBE derivatives, as it has approximately a third of the ring strain of NBE. Also, the probability of chain transfer is high, and the corresponding polymers exhibit a broad molecular weight distribution. Hillmyer et al. [61] recently demonstrated that 3-alkyl- or aryl-substituted COEs (24) can be polymerized in a regio and stereoselective manner (Figure 1.7). Upon hydrogenation, linear, low-density PE samples containing a substituent on every eighth carbon in the backbone were obtained [62, 63]. Similarly, stereoregular ethylene–vinyl alcohol copolymers were prepared by ROMP of protected COE-diol monomers [64]. Amphiphilic oligolysine-grafted polyolefines were prepared by homopolymerization of monomer 25 and copolymerization with an oligoglycol bearing COE using G3 (Figure 1.7) [65]. The resulting homopolymers were tested in DNA complexation and delivery [66]. The 5-phosphorylcholine-substituted COE monomer 26 was used to prepare homo and copolymers with monomer 27 (Figure 1.7). Both polymers exhibited aqueous assembly behavior, leading to the formation of polymersomes [67]. Other low-strained cyclic olefins have also been studied with respect to their applicability in ROMP using G1, G2, and G3 [68]. trans-COE is characterized by a ring strain that is two times higher than that of cis-COE. trans-COE and its 5-substituted derivatives have been shown to undergo ROMP using G1 in the presence of excess triphenylphosphine in a controlled and living manner [69].

Figure 1.7 COE-based monomers.

Dioxepine (28)- [70, 71], thioacetal (29)- [72], and diazaphosphineoxide (30)- [73] based cyclic monomers (Figure 1.8) were used to introduce a hydroxyl, a thiol, or an amino group at one end of the polymer chain via the “sacrificial diblock copolymer” approach. The monomers were used to make the second or third segment of a block copolymer, which upon cleavage results in the formation of the noncleavable segments with a very high degree of end group functionalization. Several other approaches to obtain (semi-)telechelic polymers via ROMP are known, and a comprehensive review covers these chemistries [74].

Figure 1.8 Monomers used in sacrificial approaches.

Cyclophanedienes 31 were polymerized with G2 in a controlled living manner to obtain a conjugated poly(phenylenevinylene) (Figure 1.9) [75–77]. The [8]-annulene 32 containing one double bond in trans configuration was also subjected to ROMP with G1 in a living manner to give a poly(phenylene vinylene) with only ortho linkages and a well-defined secondary structure [78]. The ansa-(vinylferrocene) 33 bearing a t-butyl group on every dicyclopentadienyl ligand was polymerized with G2 and Schrock-type initiators, leading to soluble poly(ferrocenylvinylene) [79].

Figure 1.9 Monomers used for the synthesis of conjugated polymers.

The ring strain is not the only driving force for the ROMP, and the thermodynamics of ROMP in terms of the Gibbs–Helmholtz equation has to be considered. Conventional highly strained monomers overcompensate the entropy loss of the polymerization by the release of the strain energy, that is, by the enthalpy contribution. Therefore, ROMP of virtually strainless olefinic macrocycles can be accomplished through the entropy-driven process known as ED-ROMP (entropy-driven ring-opening metathesis polymerization). In these cases, enthalpy effects are negligible but the entropy gain can be the driving force. The main source of the positive entropy contribution can be understood as the higher conformational flexibility of the polymer relative to the cyclic monomer [80, 81]. Recent examples of macrocyclic olefins monomers subjected to ED-ROMP are shown in Figure 1.10. The calix [4]arene-based monomer 34 was copolymerized with COE and NBE using G2 to obtain elastomeric materials. Long reaction times, that is, equilibrium conditions, were needed to guarantee a full incorporation of the unstrained macrocyclic monomer [82]. The derivatized natural sophorolipid monomer 35 was polymerized with the Grubbs initiator family, and G2 was found to give polymers with the highest molecular weight [83]. Similarly, naturally occurring bile acid-based polymers were also prepared [84]. Mayer et al. [85] used macrocycles such as 36 to prepare poly(pseudo-rotaxane)s, which are linear polymers featuring threaded macrocycles.

Figure 1.10 Macrocyclic olefins used in ED-ROMP.

1.4 Synthesis of Polymers with Complex Architectures

A good example for the versatility of ROMP in the preparation of highly functionalized polymers is PNBEs carrying permanent radical groups. Polymers carrying nitroxide free-radicals have usually been synthesized by an indirect method involving oxidation of pendant amino groups. The indirect route was adopted because of the incapability of radical-bearing monomers to undergo radical polymerization. Such polyradicals find application as cathode active materials in organic radical batteries. Several NBE- and 7-ONBE- based homopolymers featuring 2,2,5,5-tetramethyl-1-pyrrolidinyloxy (37) [86] and 2,2,6,6-tetramethylpiperidine-1-oxy (38) [87, 88] moieties as side chains have been disclosed and used in radical batteries (Figure 1.11). Related monomers were also employed in block-copolymer synthesis, and their crossover chemistry was studied in detail [89]. TEMPO-bearing monomers were also used to label brush copolymers, and their dynamics in organic solvents was studied [90]. Monomer 39 was used to prepare thermally stable homopolymers which were used as active layer in electrochromic devices. Upon applying a voltage, the color of the films tuned from light yellow to green and then to blue [91, 92]. Color switching of polymer films prepared from different monomers could also be achieved upon triggering by light [93, 94].

Figure 1.11 Monomers bearing radical moieties (37, 38) and an electrochromic group (39).

Polymers obtained via ROMP have found a wide range of application in materials chemistry such as metal-cation-based anion-exchange membranes prepared by copolymerizing a bis-cationic polymerizable ruthenium complex with DCPD [95], or lithium ion conductive membranes with low water permeation [96]. Further applications are found in (optical) sensor material research, where ROMP polymers comprising a fluorescent or phosphorescent dye are prepared. These polymers contain covalently linked dye units to the backbone, thus preventing the movement of the dye and reducing the formation of dye aggregates, which is detrimental for obtaining high luminescence quantum yields [97–101]. Limitations of this strategy have been shown by studying the luminescence and self-assembly of ROMP polymers bearing dyes, which turn on luminescence upon aggregation [102].

A versatile ROMP-based platform for the synthesis of antibacterial and cell-penetrating polycationic polymers has been built by the group of Tew. Tuning of the overall hydrophobicity and charge density leads to polymers with tailor-made properties in terms of activity against microorganisms and toxicity [103, 104]. Those polymers are water soluble and can be considered as synthetic mimics of antimicrobial peptides. These polymers can be modified to become insoluble in water, which can then be used as coatings with nonfouling properties or as additives to equip commodity polymers with contact-biocidic properties [105, 106].

Ladderphanes are built up by multiple layers of linkers covalently connected to two or more polymer chains (Figure 1.12) and can be regarded as synthetic artificial analogs to DNA. For their preparation, a relatively rigid polymer backbone is desired, which is provided by PNBEs. A further prerequisite for the preparation of ladderphanes is that the spacing between two repeating units should be about the distance typical for π–π stacking, and, for these reasons, bis-NBE based monomers as shown in Figure 1.12 have been used. Typically, G1 was used for the polymerization, resulting in the formation of a trans-isotactic polymer strand [107]. A range of ladderphanes have been prepared over the last 7 years, comprising linkers containing, for example, ferrocene [108], other transition-metal complexes (40), or planar aromatic moieties (41) [109, 110]. A comprehensive overview on the work done in the field of ladderphanes is available in the literature [111–115].

Figure 1.12 The ROMP route to ladderphanes and two examples of the monomers used.

ROMP has been used for the preparation of bottlebrush copolymers via the macromonomer approach using “grafting from” [116–118] or “grafting onto” [119, 120] techniques utilizing CBE- [57] or NBE-based monomers. Bowden prepared bottlebrush polymers from poly(l-lactide) bearing macromonomers, with G1 and G2 as the initiators [121, 122]. Furthermore, macromonomers 42 or 43 (Figure 1.13) were polymerized using G3 in a controlled living manner to obtain homopolymers as well as random and block copolymers [123, 124]. Macromonomers 42 were prepared by clicking to NBE moieties polystyrene, poly(t-butylacrylate), or poly(methylacrylate) prepared by ATRP. The concept of the bottlebrush copolymer synthesis was then extended to bivalent bottlebrush copolymers containing a poly(ethylene glycol) (PEG) arm and an azide, for the attachment of a drug after polymerization [125]. The drug can also be attached before polymerization as exemplified by the monomer 44 (Figure 1.13) containing a PEG arm, a second arm build up by a linker, a photo-cleavable group, and a drug (in this case the anticancer drug doxorubicin) [126].

Figure 1.13 Macromonomers used for the preparation of bottlebrush copolymers.

Several other research works on the synthesis of bottlebrush polymers and copolymers have also been reported [127–134], including dendronized macromonomers [40, 135]. Weck reported on the importance of the length of the spacer connecting the dendronized moiety to the polymerizable group, and found that the longer the spacer, the better the macromonomer conversion [136]. The work reported on photonic crystals made by the self-assembly of bottlebrush block copolymer blends rely on the precision with which these polymers can be made [137, 138]. Dumbbell-shaped molecular brushes were prepared by realizing a triblock copolymer architecture made with two different macromonomers via the “grafting through” approach [139]. The same macromolecular architecture can be obtained by the reaction of a homopolymer with dendritic chain-transfer agents [140].

The synthesis of block copolymers via ROMP of conventional monomers has been the focus in the last 10 years. This has included making block copolymers via sequential polymerization of different ROMP monomers as well as those made from a combination of ROMP with other polymerization techniques [74, 141] A metathesis approach has been reported involving ROMP combined with the polymerization of 1,6-heptadiynes by molybdenum or ruthenium initiators [142, 143], or with monomers allowing enyne metathesis polymerization [144]. Choi et al. [145] prepared block copolymers of NBE derivatives with a 6-heptadiyne derivative leading to an in situ crosslinking of the conjugated segment and in turn to nanoparticle formation. Moreover, a combination of ROMP and insertion polymerization of ethylene has also been reported [146].

Trimmel et al. prepared a series of amphiphilic block copolymers with different lengths of apolar and polar segments, and studied the micellization of these block copolymers in alcohol. The size of the micelles, as well as those of the core and shell could be nicely tuned [147]. In a follow-up paper, they studied the self-assembly of the block copolymers in the solid state and demonstrated how the composition polymers translates into different solid-state structures [148]. The approach was used to self-assemble platinum dyes on the nanoscale [149]. Although the syntheses of most block copolymers have been successfully accomplished, some restrictions have also been reported [89]. Particularly, monomers with the ability to strongly interact with the initiator have been shown to cause problems, which could be circumvented by polymerizing them as the second monomer [150, 23].

Grubbs et al. [151] reported a pulsed-addition protocol involving the use of a chain transfer agent, for example, a symmetrical internal cis-olefin, for terminating the ROMP and regenerating the initiator for further homo or block copolymer preparation runs.

The ruthenium initiators have also been used to conduct hydrogenations after the polymerization process. Polymers obtained from G1 or G3 have been shown to be readily hydrogenated upon addition of a base and hydrogen gas. This resulted in the decomposition of initiators and the formation of products acting as hydrogenation catalysts [152–155].

Water-dispersible amphiphilic block copolymers can be prepared by oligo ethylene glycol-substituted monomers as the hydrophilic segment. These block copolymers show a lower critical solution temperature behavior [156] and can be used for energy-transfer-based optical sensors [157]. Nguyen's group synthesized an amphiphilic block copolymer with a tosylated oligo ethylene glycol monomer and a drug (47, Figure 1.14), which self-assembled into spherical micelles with the tosyl groups at the surface. The tosyl groups were then used in a further step to attach single-stranded DNA and tumor-targeting antibodies [158]. Further work has been carried out on the synthesis of ROMP polymers for biological applications such as biodetection and signal amplification [159, 160].

Figure 1.14 Examples of interesting block copolymers.

Nanostructured materials have also been prepared by ROMP. Metal-containing block random copolymers (45, Figure 1.14) have been reported that self-assembled into cylindrical phase-separated morphology in the solid state, leading to a room-temperature ferromagnetic material or a superparamagnetic material depending on the relative amount of cobalt and iron complexes in the material [161]. Similarly, block copolymers for the stabilization of magnetic nanoparticles have been developed [162, 163]. Nano-sized domain segregation was achieved in nanowires obtained from the self-assembly of donor/acceptor-bearing block copolymers (46, Figure 1.14) in the solid state. The film prepared from the block copolymer is photoconductive suitable for applications in photovoltaic or electronic devices [164]. Similarly, random copolymers with similar donor and acceptor groups have also been disclosed [165]. Structures obtained from self-assembly possesses in selective solvents can be fixed by covalent linkages and the resulting nano-scaled materials conserve their structural identity also in nonselective solvents. Several synthetic strategies have been used for this purpose, such as the use of a cross-linking monomer for the preparation of PEG star polymers. Here, a photocleavable monomer bearing two polymerizable NBE groups was used to convert a bottlebrush copolymer into the desired nano-object [166]. Another approach involved the use of thiol–ene chemistry in which the double bonds in the polymer backbones could be used for cross-linking with multifunctional thiols [42, 167–169]. The rather apolar thiol migrates into the apolar parts of the preformed micelles, and, upon irradiation, a cross-linked polymer strand is obtained [167, 170]. Another method for inducing cross-linking is the copolymerization of monomers bearing a cinnamoyl group into amphiphilic block copolymers. The cinnamoyl groups undergo photoinduced dimerization, and thus cross-links can be established upon irradiation, after micellization [171, 172].

ROMP has also been applied in the functionalization of surfaces for tailoring properties such as surface energy and friction. Surface-initiated ring-opening metathesis polymerization (SI-ROMP) was used to attach alkylated [173, 174] and fluorinated [175–177] PNBE chains to a gold surface in order to achieve films of tuneable thickness. Earlier work investigated ionomer films on Pt-modified gold electrodes [178] and the formation of diblock copolymer brushes on gold substrates [179]. SI-ROMP on bare silicon was performed after chemomechanical treatment (scribing) with α,ω-di-olefins followed by growing NBE strands from the surface [180]. Furthermore, anodization lithography was used to prepare nano-patterned polymer brushes on silicone [181], and the resulting nano-particles were functionalized by SI-ROMP [182]. SI-ROMP has been conducted using low-strain monomers such as CPE or cyclododecene to prepare polymer brushes [183]. SI-ROMP has also been conducted on cellulose fibers [184] as well as for the preparation of functional supports and materials [185–187].

The Bowden group has studied the post-polymerization functionalization of PDCPD by bromination or epoxidation and studied the assembly of amines on the surface of the functionalized PDCPD [188–190]. The resulting materials were used as membranes to study their suitability for separating small molecules [191, 192]. Hillmyer et al. [193, 194] reported the synthesis of nano-structured PDCPD membranes by templating with reactive block copolymers. Moreover, the preparations of macroporous PDCPD of porosities up to 90%, a throughout-open porous structure [3, 195–200], and also PDCPD submicrometer fibers by electrospinning have been described [201].

1.5 Stereochemistry and Sequence Control in ROMP

Control over the stereochemistry of the double bonds in ROMP polymers has been extensively studied. Generally, the ruthenium initiator G1 gives polymers with predominantly trans double bonds, while ruthenium initiators G2 and G3 give polymers with predominantely cis double bonds [202]. However, the actual cis/trans selectivity is also dependent on the structure of the monomer. Initiators that allow control of the stereochemistry of the double bonds have been disclosed in recent years, such as a new generation of “stereogenic-at-metal” molybdenum-based initiators 48 (Figure 1.15) bearing a small axial amide ligand and a large phenolate ligand. Initiator 48 gives cis-selective and syndio-selective polymerization of NBD derivatives [203, 204]. Furthermore, rac-endo,exo-NBE-5,6-dicarboxylic acid methylester could be polymerized with the same initiator in an alternating manner, that is, the repeating units are enantiomers of one another, to give a cis-syndiotactic connectivity [205]. There are also other molybdenum-based initiators that are very useful for stereoselective ROMP, allowing the synthesis of trans-syndiotactic or cis-isotactic polymers [206, 207] although ruthenium initiators do not provide total control over cis/trans double bonds, significant improvements have recently been made [208, 209].

Figure 1.15 Molybdenum initiator used for cis- and syndio-selective ROMP.

Successful synthesis of alternating copolymers using ROMP is of great interest but also a challenging task from the mechanistic point of view. Ring-opening insertion metathesis polymerization (ROIMP) has been utilized to prepare alternating copolymers. The method involves a fast ROMP polymerization of a cyclic olefin followed by the incorporation of a linear electron-deficient di-olefin, that is, a di-acrylate, into the polymer chain by cross metathesis [210, 211]. The ring strain and steric demand of the reaction partners have been found to be crucial factors for achieving alternation in pure ROMP. Hence, copolymerization of highly strained but rather bulky NBE derivatives with COE that exhibits neither of these properties is a promising setup [212]. The strained NBE will always be consumed preferably, unless the steric hindrance is maximized, and enough COE is present in the immediate vicinity of the active center of the macroinitiator, allowing the insertion of the comparatively inactive monomer. This strategy has resulted in the preparation of materials with up to 97% alternating sequence in the polymer chain [213–217].

The synthesis of alternating ring-opening metathesis polymerization (AROMP) has also been reported by copolymerizing monomers that do not give homopolymers such as 1-cyclobutene derivatives (Figure 1.6) and cyclohexene monomers using G3 [60, 218]. However, further investigations revealed that the product also contained cyclic polymers as by-products, the proportion of which increased when a Grubbs–Hoveyda catalyst was used to maximize the back-biting reaction [219]. The methodology was extended to cationic polymers to study their antibacterial properties [220].

1.6 Conclusion

This chapter discussed only a subset of the work conducted in the field of ROMP in the last 10 years, showing that. ROMP is a privileged polymerization method for the preparation of highly functionalized polymers and is used in almost every contemporary polymer research field. ROMP is fast, functional-group tolerant, reliable, flexible, and versatile, and allows the synthesis of a broad spectrum of different polymer architectures. However, precise control of the microstructure of the polymers is still a challenge, particularly in case of ruthenium-based initiators, which, in practice, are the most commonly employed.

References

1. Moerdyk, J.P. and Bielawski, C.W. (2012)

Polymer Science: A Comprehensive Reference

, vol.

4

, Elsevier, pp. 523–550.

2. Buchmeiser, M.R. (2012)

Polymer Science: A Comprehensive Reference

, vol.

4

, Elsevier, pp. 597–632.

3. Kiesling, L.L. and Mangold, S.L. (2012)

Polymer Science: A Comprehensive Reference

, vol.

4

, Elsevier, pp. 695–717.

4. Grubbs, R.H. (2012)

Polymer Science: A Comprehensive Reference

, vol.

4

, Elsevier, pp. 21–29.

5. Buchmeiser, M.R. (2012) in

Synthesis of Polymers

, vol.

2

(eds D.A. Schlüter, C.J. Hawker, and J. Sakamoto), Wiley-VCH Verlag GmbH, Weinheim, pp. 547–586.

6. Leitgeb, A., Wappel, J., and Slugovc, C. (2010)

Polymer

,

51

, 2927–2946.

7. Sutthasupa, S., Shiotsuki, M., and Sanda, F. (2010)

Polym. J.

,

42

, 905–915.

8. Mathers, R.T. (2010) in

Handbook of Transition Metal Polymerization Catalysts

(eds R. Hoff and R.T. Mathers), John Wiley & Sons, Inc, pp. 513–536.

9. Bielawski, C.W. and Grubbs, R.H. (2009) in

Controlled and Living Polymerizations

(eds A.H.E. Müller and K. Matyjaszewski), Wiley-VCH Verlag GmbH, Weinheim, pp. 297–342.

10. Buchmeiser, M.R. (2009) in

Handbook of Ring-Opening Polymerization

(eds P. Dubois, O. Coulembier, and J.-M. Raquez), Wiley-VCH Verlag GmbH, Weinheim, pp. 197–225.

11. Bielawski, C.W. and Grubbs, R.H. (2007)

Prog. Polym. Sci.

,

32

, 1–29.

12. Fogg, D.E. and Foucault, H.M. (2007) in

Comprehensive Organometallic Chemistry III

(eds R.H. Crabtree and D.M.P. Mingos), Elsevier, Oxford, pp. 623–652.

13. Harned, A.M., Zhang, M., Vedantham, P., Mukherjee, S., Herpel, R.H., Flynn, D.L., and Hanson, P.R. (2005)

Adrichchim. Acta

,

38

, 3–16.

14. Slugovc, C., Demel, S., and Stelzer, F. (2002)

Chem. Commun.

, 2572–2573.

15. Love, J.A., Morgan, J.P., Trnka, T.M., and Grubbs, R.H. (2002)

Angew. Chem. Int. Ed.

,

41

, 4207–4209.

16. Burtscher, D., Lexer, C., Mereiter, K., Winde, R., Karch, R., and Slugovc, C. (2008)

J. Polym. Sci., Part A: Polym. Chem.

,

46

, 4630–4635.

17. Nguyen, S.T., Grubbs, R.H., and Ziller, H.W. (1993)

J. Am. Chem. Soc.

,

115

, 9858–9859.

18. Robson, D.A., Gibson, V.C., Davies, R.G., and North, M. (1999)

Macromolecules

,

32

, 6371–6373.

19. Demel, S., Riegler, S., Wewerka, K., Schoefberger, W., Slugovc, C., and Stelzer, F. (2003)

Inorg. Chim. Acta

,

345

, 363–366.

20. Bielawski, C.W. and Grubbs, R.H. (2000)

Angew. Chem. Int. Ed.

,

39

, 2903–2906.

21. Slugovc, C. (2004)

Macromol. Rapid Commun.

,

25

, 1283–1297.

22. Choi, T.-L. and Grubbs, R.H. (2003)

Angew. Chem. Int. Ed.

,

42

, 1743–1746.

23. Riegler, S., Demel, S., Trimmel, G., Slugovc, C., and Stelzer, F. (2006)

J. Mol. Catal. A: Chem.

,

257

, 53–58.

24. Breitenkamp, K. and Emrick, T. (2005)

J. Polym. Sci., Part A: Polym. Chem.

,

43

, 5715–5721.

25. Jordan, J.P. and Grubbs, R.H. (2007)

Angew. Chem. Int. Ed.

,

46

, 5152–5155.

26. Burtscher, D., Saf, R., and Slugovc, C. (2006)

J. Polym. Sci., Part A: Polym. Chem.

,

44

, 6136–6145.

27. Tuba, R., Correa da Costa, R., Bazzi, H.S., and Gladysz, J.A. (2012)

ACS Catal.

,

2

, 155–162.

28. Keitz, B.K. and Grubbs, R.H. (2009)

J. Am. Chem. Soc.

,

131

, 2038–2039.

29. Wang, D., Wurst, K., Knolle, W., Decker, U., Prager, L., Naumov, S., and Buchmeiser, M.R. (2008)

Angew. Chem. Int. Ed.

,

47

, 3267–3270.

30. Wang, D., Wurst, K., and Buchmeiser, M.R. (2010)

Chem. Eur. J.

,

16

, 12928–12934.

31. Piermattei, A., Karthikeyan, S., and Sijbesma, R.P. (2009)

Nat. Chem.

,

1

, 133–137.

32. Monsaert, S., Lozano Vila, A., Drozdzak, R., Van Der Voort, P., and Verpoort, F. (2009)

Chem. Soc. Rev.

,

38

, 3360–3372.

33. Zirngast, M., Pump, E., Leitgeb, A., Albering, J.H., and Slugovc, C. (2011)

Chem. Commun.

,

47

, 2261–2263.

34. Vidavsky, Y., Anaby, A., and Lemcoff, N.G. (2012)

Dalton Trans.

,

41

, 32–43.

35. Fürstner, A., Ackermann, L., Gabor, B., Goddard, R., Lehmann, C.W., Mynott, R., Stelzer, F., and Thiel, O.R. (2001)

Chem. Eur. J.

,

7

, 3236–3253.

36. Bielawski, C.W., Benitez, D., and Grubbs, R.H. (2002)

Science

,

297

, 2041–2044.

37. Bielawski, C.W., Benitez, D., and Grubbs, R.H. (2003)

J. Am. Chem. Soc.

,

125

, 8424–8425.

38. Boydston, A.J., Xia, Y., Kornfield, J.A., Gorodetskaya, I.A., and Grubbs, R.H. (2008)

J. Am. Chem. Soc.

,

130

, 12775–12782.

39. Xia, Y., Boydston, A.J., Yao, Y., Kornfield, J.A., Gorodetskaya, I.A., Spiess, H.W., and Grubbs, R.H. (2009)

J. Am. Chem. Soc.

,

131

, 2670–2677.

40. Boydston, A.J., Holcombe, T.W., Unruh, D.A., Fréchet, J.M., and Grubbs, R.H. (2009)

J. Am. Chem. Soc.

,

131

, 5388–5389.

41. Zhang, K. and Tew, G.N. (2012)

ACS Macro Lett.

,

1

, 574–579.

42. Zhang, K., Lackey, M.A., Cui, J., and Tew, G.N. (2011)

J. Am. Chem. Soc.

,

133

, 4140–4148.

43. Zhang, K., Lackey, M.A., Wu, Y., and Tew, G.N. (2011)

J. Am. Chem. Soc.

,

133

, 6906–6909.

44. Sutthasupa, S., Terada, K., Sanda, F., and Masuda, T. (2006)

J. Polym. Sci., Part A: Polym. Chem.

,

44

, 5337–5343.

45. Sutthasupa, S., Sanda, F., and Masuda, T. (2008)

Macromol. Chem. Phys.

,

209

, 930–937.

46. Sutthasupa, S., Terada, K., Sanda, F., and Masuda, T. (2007)

Polymer

,

48

, 3026–3032.

47. Slugovc, C., Demel, S., Riegler, S., Hobisch, J., and Stelzer, F. (2004)

Macromol. Rapid Commun.

,

25

, 475–480.

48. Haigh, D.M., Kenwright, A.M., and Khosravi, E. (2005)

Macromolecules

,

38

, 7571–7579.

49. Carrillo, A., Gujraty, K.V., Rai, P.R., and Kane, R.S. (2005)

Nanotechnology

,

16

, S416–S421.

50. Strong, L.E. and Kiessling, L.L. (1999)

J. Am. Chem. Soc.

,

121

, 6193–6196.

51. Pontrello, J.K., Allen, M.J., Underbakke, E.S., and Kiessling, L.L. (2005)

J. Am. Chem. Soc.

,

127

, 14536–14537.

52. Kolonko, E.M., Pontrello, J.K., Mangold, S.L., and Kiessling, L.L. (2009)

J. Am. Chem. Soc.

,

131

, 7327–7333.

53. Schaefer, M., Hanik, N., and Kilbinger, A.F.M. (2012)

Macromolecules

,

45

, 6807–6818.

54. Murphy, J.J., Nomura, K., and Paton, R.M. (2006)

Macromolecules

,

39

, 3147–3153.

55. Maynard, H.D., Okada, S.Y., and Grubbs, R.H. (2000)

Macromolecules

,

33

, 6239–6248.

56. Lapinte, V., de Fremont, P., Montembault, V., and Fontaine, L. (2004)

Macromol. Chem. Phys.

,

205

, 1238–1245.

57. Morandi, G., Montembault, V., Pascual, S., Legoupy, S., and Fontaine, L. (2006)

Macromolecules

,

39

, 2732–2735.

58. Morandi, G., Pascual, S., Montembault, V., Legoupy, S., Delorme, N., and Fontaine, L. (2009)

Macromolecules

,

42

, 6927–6931.

59. Lee, J.C., Parker, K.A., and Sampson, N.S. (2006)

J. Am. Chem. Soc.

,

128

, 4578–4579.

60. Song, A., Lee, J.C., Parker, K.A., and Sampson, N.S. (2010)

J. Am. Chem. Soc.

,

132

, 10513–10520.

61. Martinez, H., Miró, P., Charbonneau, P., Hillmyer, M.A., and Cramer, C.J. (2012)

ACS Catal.

,

2

, 2547–2556.

62. Kobayashi, S., Pitet, L.M., and Hillmyer, M.A. (2011)

J. Am. Chem. Soc.

,

133

, 5794–5797.

63. Zhang, J., Matta, M.E., and Hillmyer, M.A. (2012)

ACS Macro Lett.

,

1

, 1383–1387.

64. Scherman, O.A., Walker, R., and Grubbs, R.H. (2005)

Macromolecules

,

38

, 9009–9014.

65. Breitenkamp, R.B., Ou, Z., Breitenkamp, K., Muthukumar, M., and Emrick, T. (2007)

Macromolecules

,

40

, 7617–7624.

66. Breitenkamp, R.B. and Emrick, T. (2008)

Biomacromolecules

,

9

, 2495–2500.

67. Kratz, K., Breitenkamp, K., Hule, R., Pochan, D., and Emrick, T. (2009)

Macromolecules

,

42

, 3227–3229.

68. Hejl, A., Scherman, O.A., and Grubbs, R.H. (2005)

Macromolecules

,

38

, 7214–7218.

69. Walker, R., Conrad, R.M., and Grubbs, R.H. (2009)

Macromolecules

,

42

, 599–605.

70. Hilf, S., Berger-Nicoletti, E., Grubbs, R.H., and Kilbinger, A.F.M. (2006)

Angew. Chem. Int. Ed.

,

45

, 8045–8048.

71. Hilf, S., Grubbs, R.H., and Kilbinger, A.F.M. (2008)

Macromolecules

,

41

, 6006–6011.

72. Hilf, S. and Kilbinger, A.F.M. (2009)

Macromolecules

,

42

, 4127–4133.

73. Nagarkar, A.A., Crochet, A., Fromm, K.M., and Kilbinger, A.F.M. (2012)

Macromolecules

,

45

, 4447–4453.

74. Hilf, S. and Kilbinger, A.F.M. (2009)

Nat. Chem.

,

1

, 537–546.

75. Yu, C.-Y. and Turner, M.L. (2006)

Angew. Chem. Int. Ed.

,

45

, 7797–7800.

76. Yu, C.-Y., Kingsley, J.W., Lidzey, D.G., and Turner, M.L. (2009)

Macromol. Rapid Commun.

,

30

, 1889–1892.

77. Yu, C.-Y., Horie, M., Spring, A.M., Tremel, K., and Turner, M.L. (2010)

Macromolecules

,

43

, 222–232.

78. Carnes, M., Buccella, D., Decatur, J., Steigerwald, M.L., and Nuckolls, C. (2008)

Angew. Chem. Int. Ed.

,

47

, 2982–2985.

79. Masson, G., Lough, A.J., and Manners, I. (2008)

Macromolecules

,

41

, 539–547.

80. Xue, Z. and Mayer, M.F. (2009)

Soft Matter

,

5

, 4600–4611.

81. Monfette, S. and Fogg, D.E. (2009)

Chem. Rev.

,

109

, 3783–3816.

82. Yang, Y. and Swager, T.M. (2007)

Macromolecules

,

40

, 7437–7440.

83. Gao, W., Hagver, R., Shah, V., Xie, W., Gross, R.A., Ilker, M.F., Bell, C., Burke, K.A., and Coughlin, E.B. (2007)

Macromolecules

,

40

, 145–147.

84. Gautrot, J.E. and Zhu, X.X. (2009)

Macromolecules

,

42

, 7324–7331.

85. Kang, S., Berkshire, B.M., Xue, Z., Gupta, M., Layode, C., May, P.A., and Mayer, M.F. (2008)

J. Am. Chem. Soc.

,

130

, 15246–15247.

86. Qu, J., Katsumata, T., Satoh, M., Wada, J., and Masuda, T. (2007)

Macromolecules

,

40

, 3136–3144.

87. Katsumata, T., Satoh, M., Wada, J., Shiotsuki, M., Sanda, F., and Masuda, T. (2006)

Macromol. Rapid Commun.

,

27

, 1206–1211.

88. Qu, J., Katsumata, T., Satoh, M., Wada, J., and Masuda, T. (2009)

Polymer

,

50

, 391–396.

89. Binder, W.H., Pulamagatta, B., Kir, O., Kurzhals, S., Barqawi, H., and Tanner, S. (2009)

Macromolecules

,

42

, 9457–9466.

90. Xia, Y., Li, Y., Burts, A.O., Ottaviani, M.F., Tirrell, D.A., Johnson, J.A., Turro, N.A., and Grubbs, R.H. (2011)

J. Am. Chem. Soc.

,

133

, 19953–19959.

91. Lian, W.-R., Huang, Y.-C., Liao, Y.-A., Wang, K.-L., Li, L.-J., Su, C.Y., Liaw, D.J., Lee, K.-R., and Lai, J.-Y. (2011)

Macromolecules

,

44

, 9550–9555.

92. Lian, W.-R., Wang, K.-L., Jiang, J.C., Liaw, D.-J., Lee, K.-R., and Lai, J.-Y. (2011)

J. Polym. Sci., Part A: Polym. Chem.

,

49

, 3248–3259.

93. Wigglesworth, T.J. and Branda, N.R. (2005)

Chem. Mater.

,

17

, 5473–5480.

94. Griesser, T., Höfler, T., Temmel, S., Kern, W., and Trimmel, G. (2007)

Chem. Mater.

,

19

, 3011–3017.

95. Zha, Y., Disabb-Miller, M.L., Johnson, Z.D., Hickner, M.A., and Tew, G.N. (2012)

J. Am. Chem. Soc.

,

134

, 4493–4496.

96. Stone, D.A., Welna, D.T., and Allock, H.R. (2007)

Chem. Mater.

,

19

, 2473–2482.

97. Sandholzer, M., Lex, A., Trimmel, G., Saf, R., Stelzer, F., and Slugovc, C. (2007)

J. Polym. Sci., Part A: Polym. Chem.

,

45

, 1336–1348.

98. Noormofidi, N. and Slugovc, C. (2007)

Macromol. Chem. Phys.

,

208

, 1093–1100.

99. Sandholzer, M., Schuster, M., Varga, F., Liska, R., and Slugovc, C. (2008)

J. Polym. Sci., Part A: Polym. Chem.

,

46

, 3648–3661.

100. Knall, A.C., Schinagl, C., Pein, A., Noormofidi, N., Saf, R., and Slugovc, C. (2012)

Macromol. Chem. Phys.

,

213

, 2618–2627.

101. Gillissen, M.A.J., Voets, I.K., Meijer, E.W., and Palmans, A.R.A. (2012)

Polym. Chem.

,

3

, 3166–3174.

102. Niedermair, F., Noormofidi, N., Lexer, C., Saf, R., and Slugovc, C. (2011)

Polymer

,

52

, 1874–1881.

103. Tew, G.N. and Lienkamp, K. (2009)

Chem. Eur. J.

,

15

, 11784–11800.

104. Som, A., Reuter, A., and Tew, G.N. (2012)

Angew. Chem. Int. Ed.

,

51

, 980–983.

105. Kreutzwiesner, E., Noormofidi, N., Wiesbrock, F., Kern, W., Rametsteiner, K., Stelzer, F., and Slugovc, C. (2010)

J. Polym. Sci., Part A: Polym. Chem.

,

48

, 4504–4514.

106. Colak, S. and Tew, G.N. (2012)

Langmuir

,

28

, 666–675.

107. Lin, W.-Y., Wang, H.-W., Liu, Z.-C., Xu, J., Chen, C.-W., Yang, Y.-C., Huang, S.-L., Yang, H.–.C., and Luh, T.-Y. (2007)

Chem. Asian J.

,

2

, 764–774.

108. Yang, H.-C., Lin, S.-Y., Yang, H.-C., Lin, C.-L., Tsai, L., Huang, S.-L., Chen, I.-W.P., Chen, C.-H., Jin, B.-Y., and Luh, T.-Y. (2006)

Angew. Chem. Int. Ed.

,

45

, 726–730.

109. Chou, C.-M., Lee, S.-L., Chen, C.-H., Biju, A.T., Wang, H.-W., Wu, Y.-L., Zhang, G.-F., Yang, K.-W., Lim, T.-S., Huang, M.-J., Tsai, P.-Y., Lin, K.-C., Huang, S.-L., Chen, C.-H., and Luh, T.-Y. (2009)

J. Am. Chem. Soc.

,

131

, 12579–12585.