RAFT Polymerization E-Book

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

Seitenzahl: 2133

Veröffentlichungsjahr: 2021

Beschreibung

Explore this one-stop resource for reversible addition-fragmentation chain transfer polymerization from a leading voice in chemistry 

RAFT Polymerization: Methods, Synthesis and Applications delivers a comprehensive and insightful analysis of reversible addition-fragmentation chain transfer polymerization (RAFT) and its applications to fields as diverse as material science, industrial chemistry, and medicine. This one-stop resource offers readers a detailed synopsis of the current state of RAFT polymerization.  

This text will inspire further research and continue the drive to an ever-increasing range of applications by synthesizing and explaining the more central existing literature on RAFT polymerization. It contains a beginner’s guide on how to do a RAFT polymerization before moving on to much more advanced techniques and concepts, like the kinetics and mechanisms of the RAFT process. The distinguished editors have also included resources covering the four major classes of RAFT agents and recent developments in processes for initiating RAFT polymerization. Readers will also benefit from the inclusion of: 

• A thorough introduction to the mechanisms, theory, and mathematical modeling of RAFT 
• Explorations of RAFT agent design and synthesis, dithioesters, dithiobenzoates, trithiocarbonates, xanthates, dithiocarbamates, macromonomer RAFT, and RAFT copolymerization 
• Discussions of a variety of RAFT architectures, including multiblocks, combs, hyperbranched polymers, and stars 
• Treatments of end group transformation, cationic RAFT, high-throughput RAFT, and RAFT in continuous flow 
• An examination of sequence defined polymers by RAFT 

Perfect for organic chemists, polymer chemists, and materials scientists, RAFT Polymerization: Methods, Synthesis and Applications will also earn a place in the libraries of chemical engineers seeking a one-stop reference for this method of controlled radical polymerization with a wide range of applications in multiple areas. 

Leseprobe

Table of Contents

Cover

Title Page

Title Page

Copyright

Volume 1

Preface

Acknowledgements

1 Overview of RAFT Polymerization

References

2 Terminology in Reversible Deactivation Radical Polymerization (RDRP) and Reversible Addition–Fragmentation Chain Transfer (RAFT) Polymerization

2.1 Terminology for Reversible Deactivation Radical Polymerization (RDRP)

2.2 Terminology in Reversible Addition–Fragmentation Chain Transfer (RAFT) Polymerization

2.3 Terminology That Is Not Ratified by IUPAC

References

3 How to Do a RAFT Polymerization

3.1 Introduction

3.2 IP Landscape

3.3 General Experimental Conditions

3.4 RAFT Polymerization of Styrene

3.5 RAFT Polymerization of Methacrylates and Acrylates

3.6 RAFT Polymerization of Acrylamides and Methacrylamides

3.7 RAFT Polymerization of Vinyl Esters and Vinyl Amides

3.8 Copolymers

3.9 Block Copolymers

3.10 Conclusion

References

4 Kinetics and Mechanism of RAFT Polymerizations

4.1 Introduction

4.2 Ideal RAFT Polymerization Kinetics

4.3 Pulsed Laser Experiments in Conjunction with EPR Detection

4.4 Quantum Chemical Calculations of the RAFT Equilibrium

4.5 Xanthate‐, Trithiocarbonate‐ and Dithiobenzoate‐Mediated Polymerizations

4.6 Summary of Results and Concluding Remarks

References

5 RAFT Polymerization: Mechanistic Considerations

5.1 Introduction

5.2 Role of the R Group

5.3 Role of the Z Group

5.4 Light Effects on the Rate of Polymerization

5.5 Conclusion

References

6 Quantum Chemical Studies of RAFT Polymerization

6.1 Introduction

6.2 Methodology

6.3 Computational Modelling of RAFT Kinetics

6.4 Structure–Reactivity Studies

6.5 Outlook

References

Note

7 Mathematical Modelling of RAFT Polymerization

7.1 Introduction

7.2 Deterministic Modelling Techniques (DMTs)

7.3 Stochastic Modelling Techniques (SMTs)

7.4 Hybrid Methods

7.5 Specific or Novel Polymerization Processes

7.6 Closing Remarks

Acknowledgments

References

Notes

8 Dithioesters in RAFT Polymerization

8.1 Introduction

8.2 Mechanism of RAFT Polymerization with Dithioester Mediators

8.3 Choice of RAFT Agents

8.4 Synthesis of Dithioester RAFT Agents

8.5 Monomers for Dithioester‐Mediated RAFT Polymerization

8.6 Cyclopolymerization

8.7 Ring‐Opening Polymerization

8.8 RAFT Crosslinking Polymerization

8.9 RAFT Self‐condensing Vinyl Polymerization

8.10 RAFT‐Single‐Unit Monomer Insertion (RAFT‐SUMI) into Dithioesters

8.11 Dithioesters in Mechanism‐Transformation Processes

8.12 Thermally Initiated RAFT Polymerization with Dithioesters

8.13 Photoinitiated RAFT with Dithioesters

8.14 Redox‐Initiated RAFT with Dithioesters

8.15 Reaction Conditions and Side Reactions of Dithioesters

8.16 RAFT Emulsion/Miniemulsion Polymerization Mediated by Dithioesters

8.17 Dithioester Group Removal/Transformation

Abbreviations

References

9 Trithiocarbonates in RAFT Polymerization

9.1 Introduction

9.2 Mechanism of RAFT Polymerization with Trithiocarbonate Mediators

9.3 Choice of Homolytic Leaving Group R for Trithiocarbonate RAFT Agents

9.4 Choice of Activating Group ‘Z’ for Trithiocarbonate RAFT Agents

9.5 Symmetric Trithiocarbonates

9.6 Non‐symmetric Trithiocarbonates

9.7 Functional Trithiocarbonates

9.8 Synthesis of Trithiocarbonates

9.9 Polymer Syntheses with Trithiocarbonates

9.10 Macromonomers

9.11 Cyclopolymerization

9.12 Radical Ring‐Opening Polymerization

9.13 RAFT Crosslinking Polymerization

9.14 RAFT Self‐condensing Vinyl Polymerization

9.15 RAFT‐Single‐Unit Monomer Insertion (RAFT‐SUMI) into Trithiocarbonates

9.16 Trithiocarbonates in Mechanism Transformation Processes

9.17 Photoinitiated RAFT with Trithiocarbonates

9.18 Redox‐Initiated RAFT with Trithiocarbonates

9.19 RAFT Emulsion/Miniemulsion/Dispersion Polymerization Mediated by Trithiocarbonates

9.20 Reaction Conditions and Side Reactions of Trithiocarbonates

9.21 Trithiocarbonate Group Removal/Transformation

9.22 Conclusions and Outlook

Abbreviations

References

10 Xanthates in RAFT Polymerization

10.1 Introduction

10.2 Synthesis of RAFT/MADIX Agents

10.3 Experimental Conditions

10.4 Kinetics

10.5 Monomers

10.6 Macromolecular Architectures

10.7 Methodologies for Xanthate End‐Group Removal

10.8 Industrial Applications of RAFT/MADIX Polymerization

10.9 Conclusion

References

11 Dithiocarbamates in RAFT Polymerization

11.1 Introduction

11.2 Dithiocarbamate Transfer Constants

11.3 Dithiocarbamates and RAFT Polymerization

11.4 Monomers for RAFT Polymerization

11.5 Synthesis of Dithiocarbamate RAFT Agents

11.6 Activity of Dithiocarbamate RAFT Agents

11.7 Dithiocarbamates in RAFT Emulsion Polymerization

11.8 Dithiocarbamates in Mechanism‐Transformation Processes

11.9 Dithiocarbamate Group Removal/Transformation

11.10 Dithiocarbamate Z′Z″NC(S)S groups

11.11 Conclusions

Acknowledgements

Abbreviations

References

12 PhotoRAFT Polymerization

12.1 Introduction

12.2 Photoinitiation

12.3 Photoiniferter Polymerizations

12.4 Applications

12.5 Conclusions and Outlook

References

Volume 2

13 Redox‐Initiated RAFT Polymerization and (Electro)chemical Activation of RAFT Agents

13.1 Introduction

13.2 Redox Initiation

13.3 Chemical Activation of RAFT Agents

13.4 Electrochemical Activation of RAFT Agents

13.5 Electro‐reduction of Radical Initiators

13.6 Conclusions and Perspectives

Acknowledgement

References

14 Considerations for and Applications of Aqueous RAFT Polymerization

14.1 Introduction

14.2 Chain Transfer Agents

14.3 Initiation

14.4 Deoxygenation Methods

14.5 Polymerization‐Induced Self‐assembly

14.6 Grafting from Biomolecules

References

15 RAFT‐Mediated Polymerization‐Induced Self‐Assembly (PISA)

†

15.1 Introduction

15.2 History/Origin of PISA

15.3 PISA Process

15.4 Reactive/Functional Nano‐objects

15.5 Control over the Particle Morphology

15.6 Applications

15.7 Conclusions

Acknowledgements

References

Note

16 RAFT‐Functional End Groups: Installation and Transformation

16.1 Introduction

16.2 Functionalization and Transformation of RAFT Polymers via the R‐group

16.3 Thiocarbonylthio End Group Removal and Transformation

16.4 Summary

References

17 Sequence‐Encoded RAFT Oligomers and Polymers

References

18 Synthesis and Application of Reactive Polymers via RAFT Polymerization

18.1 Introduction

18.2 N‐Hydroxysuccinimide (NHS)

18.3 Pentafluorophenyl (PFP) Ester and Its Derivatives

18.4

p

‐Nitrophenyl Esters and Their Derivatives

18.5 Miscellaneous Activated Ester Functional Group Transformations

18.6 Acetone Oxime (AO)

18.7 Salicylic Acid (SA)

18.8

p

‐Dialkylsulfonium Phenoxy Ester (DASPE)

18.9 1,1,1,3,3,3‐Hexafluoroisopropanol (HFIP)

18.10 Di(Boc)‐Acrylamide (DBAm)

18.11 Acyl Chloride

18.12 Alkyl Halide

18.13 Trichlorotriazine (TCT)

18.14 Isocyanate (NCO)

18.15 Azlactone

18.16 Anhydride

18.17 Thiolactone

18.18 Thiol Exchange (Disulphide)/Michael Addition/Thiol–Ene

18.19 Epoxide

18.20 Diels–Alder Cycloaddition

18.21 Triazolinedione

18.22 Carbonyl Groups and their Derivatives

18.23 Copper‐Catalysed Azide–Alkyne Cycloaddition (CuAAC)

18.24 Strain‐Promoted Azide–Alkyne Cycloaddition (SPAAC)

18.25 Nitrone– and Nitrile Oxide–Alkyne Cycloadditions (SPANOC/SPANC)

18.26 Cross‐coupling Reactions

18.27 Boronic Acid/Diol Condensation

18.28 Multicomponent Reactions (MCR)

18.29 Metal–Ligand Coordination

18.30 Bioapplications of Reactive Polymers

18.31 Drug Delivery

18.32 Bio‐conjugation

18.33 Surface/Particle Modification

18.34 Conclusion and Outlook

References

19 RAFT Crosslinking Polymerization

19.1 Introduction

19.2 Structure and Characteristics of Polymer Networks

19.3 RAFT Crosslinking Polymerization

19.4 Synthesis of Polymer Networks by RAFT Copolymerization of Vinyl/Multivinyl Monomers in Supercritical Carbon Dioxide as Green Solvent

19.5 Modelling of Polymer Network Formation

19.6 Closing Remarks

Acknowledgements

References

20 Complex Polymeric Architectures Synthesized through RAFT Polymerization

20.1 Introduction

20.2 RAFT Synthesis of Block Copolymers

20.3 Gradient Copolymers

20.4 Cyclic Polymers

20.5 Star‐Shaped Polymers

20.6 Graft Polymers

20.7 Hyperbranched Polymers

20.8 Conclusion

Acknowledgements

References

21 Star Polymers by RAFT Polymerization

21.1 Star Polymers

21.2 Synthesis of Star Polymers via RAFT Polymerization

21.3 Application of Star polymers

21.4 Conclusion

References

22 Surface and Particle Modification via RAFT Polymerization: An Update

22.1 Introduction

22.2 Complex Brush Architectures

22.3 Bioconjugation and Stimuli‐responsive Polymer Brushes

22.4 Advanced Composites

22.5 Shaped Polymer‐Grafted Particles

22.6 Conclusion

Acknowledgements

References

23 High‐Throughput/High‐Output Experimentation in RAFT Polymer Synthesis

23.1 Introduction

23.2 Fundamental Experimentation and Limitations of HT/HO‐E in RAFT Polymer Synthesis

23.3 HT/HO‐E Kinetic Investigations

23.4 Utilization of HT/HO‐E for the RAFT Synthesis of Polymer Libraries

23.5 Applications of RAFT Polymer Libraries in Nanomedicine and Drug Delivery Systems

23.6 Conclusions

Acknowledgements

References

24 An Industrial History of RAFT Polymerization

24.1 Introduction

24.2 Macromonomer RAFT Polymerization

24.3 Thiocarbonylthio‐RAFT Polymerization

References

25 Cationic RAFT Polymerization

25.1 Introduction

25.2 Background and Overview of Cationic RAFT Polymerizations

25.3 Design of Cationic RAFT or DT Polymerizations

25.4 Design of Well‐Defined Polymers by Cationic RAFT or DT Polymerizations

25.5 Summary and Outlook for Cationic RAFT or DT Polymerizations

References

Index

End User License Agreement

List of Tables

Chapter 2

Table 2.1 IUPAC recommendations on terminology for reversible deactivation r...

Table 2.2 IUPAC recommendations on terminology for reversible addition–fragm...

Table 2.3 Additional terminology for reversible addition–fragmentation chain...

Chapter 3

Table 3.1 A list of selected commonly used RAFT agents with their suitabilit...

Table 3.2 Summary of field restrictions for commonly used RAFT agents.

Table 3.3 Bulk RAFT polymerization of un‐purified commercial MMA with 4‐cyan...

Table 3.4 Molecular weight/conversion data for the bulk thermal polymerizati...

Table 3.5 Molecular weights and molar mass dispersities for PMMA formed by p...

Table 3.6 RAFT polymerization of BnMA using

1

as a chain transfer agent.

Table 3.7 RAFT copolymerization of triphenylmethyl methacrylate

34

and methac...

Table 3.8 Preparation of poly(

N

-(2-hydroxypropyl)methacrylamide)-

b

-poly(benz...

Chapter 4

Table 4.1 Summary of the addition rate coefficients

k

ad

and fragmentation rat...

Chapter 5

Table 5.1 Transfer constants of various dithiobenzoates in MMA polymerizatio...

Table 5.2 Estimated monomer addition rate coefficients for initiator‐derived...

Table 5.3 Main classes of transfer agents suitable for RAFT polymerization a...

Chapter 6

Table 6.1 Effect of R′ on the calculated enthalpies (Δ

H

), entropies...

Table 6.2 Effect of R, Z, and R′ on the calculated equilibrium constants...

Table 6.3 Calculated addition (

k

add

), fragmentation (

k

frag

), and equilibrium...

Chapter 7

Table 7.1 Polymerization scheme for RAFT polymerization.

Table 7.2 Steps used in Predici™ for kinetic modelling of RAFT polymerizatio...

Table 7.3 Implementation of Model 1 in Predici.

Chapter 8

Table 8.1 Transfer coefficients of dithioester RAFT agents ZC(S)SR in RAF...

Table 8.2 Transfer coefficients of dithioester macroRAFT agents ZC(S)SP

n

...

Table 8.3 Values of the RAFT equilibrium coefficients with dithioesters.

Table 8.4 RAFT polymerizations with popular or commercially available aromat...

Table 8.5 Functional dithioester RAFT agents.

Table 8.6 Bis‐dithioester RAFT agents.

Table 8.7 RAFT agents and RAFT polymerizations – aliphatic dithioester RAFT ...

Table 8.8 RAFT agents and RAFT polymerizations –

bis

‐dithioester RAFT agents ...

Table 8.9 Methacrylate monomers subjected to RAFT polymerization.

Table 8.10 Methacrylamide derivatives subjected to RAFT polymerization.

Table 8.11 Other 1,1‐disubsituted monomers subjected to RAFT polymerization.

Table 8.12 Acrylate monomers subjected to RAFT polymerization.

Table 8.13 Acrylamide derivatives subjected to RAFT polymerization.

Table 8.14 Styrene derivatives subjected to RAFT polymerization.

Table 8.15 Monosubstituted LAMs and IAMs (vinyl monomers).

Table 8.16 Monomers with reactive functionality.

Table 8.17 Macromonomers subjected to RAFT polymerization.

Table 8.18 Monomers used in experiments on dithioester‐mediated RAFT cyclopo...

Table 8.19 Monomers used in experiments on dithioester‐mediated RAFT ring op...

Table 8.20 Crosslinking monomers.

Table 8.21 Preparation of model co‐networks by RAFT polymerization with ‘R’‐...

Table 8.22 RAFT monomers for self‐condensing vinyl polymerization.

Table 8.23 Dithioester end‐group transformation by reaction with nucleophile...

Table 8.24 Dithioester group removal by radical‐induced reactions (coupling ...

Table 8.25 Dithioester group removal by radical‐induced reduction.

Table 8.26 Dithioester group removal by oxidation.

Chapter 9

Table 9.1 Transfer coefficients for initial trithiocarbonates in RAFT polyme...

Table 9.2 Values of the RAFT equilibrium coefficient for trithiocarbonates.

Table 9.3 RAFT polymerizations with symmetrically substituted trithiocarbona...

Table 9.4 RAFT polymerizations with symmetrically substituted, Z‐connected, ...

Table 9.5 RAFT polymerizations with symmetrically substituted, R‐connected, ...

Table 9.6 RAFT polymerizations with non‐symmetric trithiocarbonate RAFT agen...

Table 9.7 RAFT polymerizations with functional trithiocarbonates derived fro...

Table 9.8 RAFT polymerizations with functional trithiocarbonates derived fro...

Table 9.9 Methacrylate monomers subjected to RAFT polymerization.

Table 9.10 Methacrylamide derivatives subjected to RAFT polymerization.

Table 9.11 Other 1,1‐disubstituted monomers subjected to RAFT polymerization...

Table 9.12 Acrylate monomers subjected to RAFT polymerization.

Table 9.13 Acrylamide derivatives subjected to RAFT polymerization.

Table 9.14 Styrene derivatives subjected to RAFT polymerization.

Table 9.15 Vinyl derivatives subjected to trithiocarbonate‐mediated RAFT pol...

Table 9.16 Monomers with reactive functionality used in trithiocarbonate‐med...

Table 9.17 Macromonomers subjected to RAFT polymerization.

Table 9.18 Monomers subjected to RAFT cyclopolymerization.

Table 9.19 Monomers used in trithiocarbonate‐mediated RAFT ring‐opening poly...

Table 9.20 Examples of multiolefinic monomers used in RAFT Crosslinking poly...

Table 9.21 RAFT monomers for self‐condensing vinyl polymerization.

Table 9.22 RAFT monomers for synthesis of combs and defined networks.

Table 9.23 Molecular weight and conversion data obtained in semi‐batch emuls...

Table 9.24 Trithiocarbonate group removal by radical‐induced coupling.

Table 9.25 Trithiocarbonate‐group removal by radical‐induced disproportionat...

Table 9.26 Trithiocarbonate group removal by radical‐induced reduction.

Table 9.27 Trithiocarbonate group removal through reaction with nucleophiles...

Table 9.28 End‐group removal by thermolysis.

Table 9.29 Trithiocarbonate group removal by oxidation.

Chapter 10

Table 10.1 Xanthates (ZOC(=S)SR) used as RAFT agents.

Table 10.2 Monomers compatible with the RAFT/MADIX process.

Chapter 11

Table 11.1 Estimates of apparent transfer coefficients (

C

tr

app

) for dithioca...

Table 11.2 RAFT polymerization with dithiocarbamate RAFT agents.

Table 11.3 RAFT polymerization with switchable dithiocarbamate RAFT agents.

Table 11.4 Methacrylate and other 1,1‐disubstituted monomers subjected to RA...

Table 11.5 Acrylate and acrylamide derivatives subjected to RAFT polymerizat...

Table 11.6 Styrene derivatives subjected to RAFT polymerization with dithioc...

Table 11.7 Vinyl monomers subjected to RAFT polymerization.

Table 11.8 Examples of syntheses of dithiocarbamates by alkylation of a carb...

Table 11.9 Synthesis of 1‐phenylethyl or benzyl dithiocarbamates.

Table 11.10 Synthesis of dithiocarbamate RAFT agents by reaction of dialkyld...

Table 11.11 Examples of syntheses of tertiary carboxyl‐functional dithiocarb...

Table 11.12 End‐group removal by radical‐induced coupling.

Table 11.13 End‐group removal by radical‐induced disproportionation.

Table 11.14 End‐group removal by radical‐induced reduction.

Table 11.15 End‐group removal by reaction with nucleophiles.

Table 11.16 End‐group removal by copper‐promoted cross‐coupling.

Table 11.17 Dithiocarbamate RAFT agent Z′Z″NC(S)S groups.

Chapter 12

Table 12.1 RAFT agent compatibility of representative photoredox catalysts f...

Chapter 13

Table 13.1 Onset potential values for the reduction of electrochemically cha...

Table 13.2 Cathodic peak and onset potential value for the reduction of comm...

Chapter 19

Table 19.1 Abbreviations employed for monomers and chemical compounds.

Table 19.2 RAFT agents used in the synthesis of polymer networks.

Table 19.3 Multifunctional RAFT agents used in the synthesis of polymer netw...

Table 19.4 Swelling index (SI) and

M

c

results for conventional RP and RAFT co...

Table 19.5 Systems properties.

Table 19.6 Polymerization scheme for the trifunctional approach.

Table 19.7 Polymerization scheme for the RAFT copolymerization with crosslin...

Table 19.8 List of parameters used in model equations.

Chapter 21

Table 21.1 Summary of UHMW PDMA star polymers synthesized via photoiniferter...

Chapter 24

Table 24.1 Macromonomer RAFT agent α‐methylvinyl end groups, ZC(=CH...

Table 24.2 Patents relating to macromonomer RAFT polymerization.

Table 24.3 Patents relating to forming macromonomers by catalytic chain tran...

Table 24.4 Patents relating to forming macromonomers by addition–fragmentati...

Table 24.5 Patents relating to forming macromonomers

1‐3

by other metho...

Table 24.6 Thiocarbonylthio-RAFT agent ZC(=S)S- groups described in the pate...

Table 24.7 Patents relating to the development of thiocarbonylthio‐RAFT poly...

Table 24.8 RAFT agents that have been produced/used on a large scale by indu...

Table 24.9 Patents relating to applications of thiocarbonylthio‐RAFT polymer...

Table 24.10 Patents disclosing methods for RAFT end‐group removal/transforma...

Chapter 25

Table 25.1

M

n

,

M

w

/

M

n

, chain transfer constants...

List of Illustrations

Chapter 1

Figure 1.1 Cumulative publications relating to RAFT polymerization for the p...

Figure 1.2 Publication rate for RAFT polymerization using different classes ...

Chapter 2

Scheme 2.1 Simplified mechanism for reversible addition–fragmentation chain ...

Chapter 3

Scheme 3.1 Mechanism for reversible addition–fragmentation chain transfer (R...

Figure 3.1 Polymer architectures amenable to RAFT polymerization.

Figure 3.2 Guidelines for the selection of RAFT agents for various polymeriz...

Figure 3.3 Comparison of conventional and RAFT polymerization. (a) Thermal p...

Figure 3.4 Examples of functional styrenic monomers amenable to RAFT polymer...

Figure 3.5 Selection of RAFT agents described in experimental procedures. RA...

Figure 3.6 Examples of functional methacrylate and acrylate monomers amenabl...

Figure 3.7 Examples of functional methacrylamide and acrylamide monomers ame...

Figure 3.8 Examples of functional vinylic monomers amenable to RAFT polymeri...

Chapter 4

Scheme 4.1 Pre‐equilibrium and main equilibrium RAFT processes.

Figure 4.1 SP–PLP–EPR setup entirely consisting of commercially available in...

Scheme 4.2 (a)

S

,

S

′‐Bis(methyl 2‐propionate) trithiocarbonate (BMPT), (b)

S

-...

Figure 4.2 Time evolution, after applying a single laser pulse at

t

 = 0, of ...

Figure 4.3 SP‐PLP‐EPR traces of INT* and P* species after applying a laser s...

Figure 4.4 Inhibition as well as rate retardation during RAFT polymerization...

Scheme 4.3 (a) Dithiobenzoate RAFT agents under investigation (left) and res...

Figure 4.5 Comparison of simulated and experimental concentration vs. time t...

Figure 4.6 Section of the EPR spectrum used for

determination;

black line

:...

Figure 4.7 Comparison of simulated and experimental concentration vs. time p...

Figure 4.8 Comparison of simulated and experimental concentration vs. time p...

Figure 4.9 Ratio of intermediate radical and propagating radical concentrati...

Figure 4.10 Ratio of intermediate radical and propagating radical concentrat...

Scheme 4.4 Main equilibrium situation with dithiobenzoate‐mediated RAFT poly...

Scheme 4.5 Cross‐termination reaction [11].

Scheme 4.6 Resonance structures of the macroINT* species

4

[11].

Scheme 4.7 Examples of the P

k

–Int species

5

produced by reaction of

4

with p...

Scheme 4.8 ‘Missing step’ reaction illustrated for one out of a multitude of...

Scheme 4.9 Two examples of potential ‘missing step’ pathways [44].

Scheme 4.10 Kinetic scheme underlying the

PREDICI

simulations with the ‘miss...

Figure 4.11 Catalytic cycle of radical termination mediated by a dithiobenzo...

Scheme 4.11 Kinetic scheme for the model system PE*–PEDB reacting in toluene...

Scheme 4.12 Kinetic scheme for the model system CIP*–CPDB; CT1: cross‐termin...

Figure 4.12 Experimental and simulated concentration vs. time traces for pro...

Scheme 4.13 Structure of the ‘missing step’ product MMADB

MS

from reaction of...

Scheme 4.14 Structure of the cross‐termination product CT1 (dimethyl 2,2′‐(3...

Chapter 5

Scheme 5.1 Processes unique to RAFT polymerization: initial chain transfer o...

Figure 5.1 Double log plot of chain transfer agent concentration against mon...

Scheme 5.2 Formation of block copolymers via RAFT. Where the polymeric radic...

Figure 5.2 (a) Chain transfer reactions for (i) cumyl phenyldithioacetate an...

Figure 5.3 (a) Relative concentrations of methyl protons of dithiobenzoate s...

Scheme 5.3 Proposed acid‐catalysed cyano‐hydrolysis mechanism for 4‐cyanopen...

Figure 5.4 (a) Initial chain transfer reaction for RAFT polymerization of MM...

Scheme 5.4 Order of chain transfer efficiency for various thiocarbonylthio c...

Scheme 5.5 Zwitterionic canonical forms of (a) xanthates and (b)

N,N

‐dialkyl...

Scheme 5.6 Side fragmentation in the RAFT‐mediated polymerization of ethylen...

Figure 5.5 (a) Molecular weight distributions of polyethylene produced in a ...

Scheme 5.7 Application of

N

‐(4‐pyridinyl)‐

N

‐methyldithiocarbamates for RAFT ...

Scheme 5.8 Relative activity of dithiocarbamate ‘ZC(S)S–’ groups in RAFT po...

Figure 5.6 Molecular weight distributions for poly(

N,N

‐dimethylacrylamide) m...

Scheme 5.9 Intermediate radical termination as proposed by Monteiro and de B...

Scheme 5.10 Model compounds prepared in the study of Kwak et al. [106] demon...

Scheme 5.11 (a) Reaction of the three‐armed star formed via intermediate rad...

Figure 5.7 (a) Comparison between the molecular weight distributions suggest...

Figure 5.8 Styrene conversion rates (min

−1

) vs. fractional conversion ...

Figure 5.9 (a) Experimental procedure used to probe 2‐phenylprop‐2‐yl dithio...

Figure 5.10 (a) Aqueous size exclusion chromatograms (

refractive index

[

RI

] ...

Figure 5.11 Theoretically predicted concentrations of living and dead chain ...

Figure 5.12 Aqueous size exclusion chromatograms (with RI detection) for the...

Figure 5.13 RAFT reaction of MMA with 4‐cyano‐4‐((dodecylthio)carbonothio)pe...

Chapter 6

Figure 6.1 The effect of chain length (

n

) on the equilibrium constant (

K

; l ...

Scheme 6.1 Set of addition–fragmentation reactions to be included in a compl...

Figure 6.2 Experimental (McCleary et al. [58], symbols) and simulated (Coote...

Figure 6.3 The effect of chain length (

n

) on the equilibrium constant (

K

; l ...

Scheme 6.2 Competitive β‐scission processes in xanthate‐media...

Scheme 6.3 Possible reversible and irreversible termination reactions of the...

Scheme 6.4 Reaction scheme for

ab initio

kinetic modelling of cyanoisopropyl...

Figure 6.4 State correlation diagram for radical addition to double bonds [3...

Figure 6.5 State correlation diagrams showing the qualitative effect on the ...

Figure 6.6 Effect of Z group on fragmentation efficiency, RAFT agent stabili...

Figure 6.7 Effect of R on RAFT agent stability, R˙ stabili...

Figure 6.8 Steric (

θ

), polar (

ionization potential

[

IP

], EA), and reson...

Chapter 7

Figure 7.1 Evolution of average characteristics using different kinetic theo...

Figure 7.2 Comparison of Models A and B (see text) against experimental data...

Figure 7.3 (a) Comparison between experimental (solid lines) and simulated (...

Figure 7.4 MWDs for the RAFT polymerization of Sty obtained by the PGF (symb...

Figure 7.5 4‐vinylbenzyl 1

H

‐imidazole‐4‐carbodithioate.

Chapter 8

Figure 8.1 Publication rate of papers on RAFT polymerization using various c...

Scheme 8.1 Mechanism of RAFT polymerization with exogenous initiator.

Figure 8.2 Values of apparent transfer coefficients (

C

tr

app

) for aromatic di...

Figure 8.3 Structural features of thiocarbonylthio RAFT agent and the interm...

Figure 8.4 Rate of journal publication on aryl dithioesters

1a

in the period...

Figure 8.5 (a) Effect of ZC(S) group and (b) R group on the activity of di...

Scheme 8.2 RAFT polymerization mediated by a ‘R‐connected’ bis‐dithioester t...

Scheme 8.3 RAFT polymerization mediated by a ‘Z‐connected’ bis‐dithioester t...

Figure 8.6 Rate of journal publication on aliphatic dithioesters

1b

in the p...

Scheme 8.4 Major methods for dithioester RAFT agent synthesis. RX, alkylatin...

Scheme 8.5 Formation of a P3HT macroRAFT agent by

N

,

N′

‐dicyclohexylcar...

Scheme 8.6 Examples of chain‐end functionalization by RAFT‐SUMI of MAH into ...

Scheme 8.7 Potential reaction pathways during an ESARA process used to form ...

Scheme 8.8 Mechanism for initiation of RAFT polymerization without an exogen...

Scheme 8.9 Transformation of polymers with dithiobenzoate end‐group (PEGA‐DB...

Scheme 8.10 Dithioester group (Z = aryl or alkyl) removal by radical‐induced...

Scheme 8.11 Hetero‐Diels–Alder process with 2‐pyridyl dithioester as dienoph...

Scheme 8.12 Proposed pathways for reaction of a dithioester with diazomethan...

Scheme 8.13 Sequential SUMI of styrene (St) and copper‐promoted cross‐coupli...

Chapter 9

Figure 9.1 Structural features of trithiocarbonate RAFT agents and the inter...

Figure 9.2 Publication rate for RAFT polymerization using different classes ...

Scheme 9.1 Mechanism of RAFT polymerization with non‐symmetric trithiocarbon...

Scheme 9.2 Mechanism of RAFT polymerization with symmetric trithiocarbonates...

Figure 9.3 Structures of some trithiocarbonates referred to in Table 9.1 (ot...

Figure 9.4 (a) Effect of R′SC(S) group on non‐symmetric trithiocarbonates ...

Scheme 9.3 Process of RAFT polymerization with symmetric trithiocarbonates (

Scheme 9.4 Process of RAFT polymerization with R‐connected bis‐RAFT agents (...

Figure 9.5 Publication rate for RAFT polymerization for the three most popul...

Scheme 9.5 RAFT cyclocopolymerization of DVE/MAH.

Scheme 9.6 Example of chain‐end functionalization by RAFT‐SUMI of allyl mono...

Scheme 9.7 Example of formation of macroRAFT agents by RAFT‐SUMI of a macrom...

Scheme 9.8 Example of RAFT‐

Ŧ

‐ROP involving RAFT polymerization of HPMAm...

Scheme 9.9 Proposed mechanism for loss of trithiocarbonate functionality fro...

Scheme 9.10 Proposed mechanism for nitrile hydrolysis for trithiocarbonates ...

Scheme 9.11 Trithiocarbonate group removal by various radical‐induced reacti...

Scheme 9.12 Trithiocarbonate group loss by Chagaev elimination (e.g. PSt). E

Scheme 9.13 Trithiocarbonate group loss by homolysis followed by backbiting ...

Scheme 9.14 Trithiocarbonate group loss by homolysis followed by unzipping (...

Chapter 10

Scheme 10.1 Atom transfer radical addition–fragmentation for the synthesis o...

Scheme 10.2 Proposed mechanism for xanthate‐mediated PET‐RAFT polymerization...

Scheme 10.3 Rearrangement and Z‐group fragmentation occurring during the pol...

Scheme 10.4 Synthetic route to thiolactone‐containing RDRP agents for contro...

Scheme 10.5 Synthesis of amphiphilic block copolymer PNVTri‐

b

‐PNVCbz and the...

Scheme 10.6 Synthesis of P(CTFE‐

alt

‐EVE)‐

b

‐PEVE and PEVE‐

b

‐P(CTFE‐

alt

‐EVE) b...

Scheme 10.7 Preparation of PVAc and PNVP cyclic polymers by RAFT polymerizat...

Scheme 10.8 Schematic representation of the general synthetic approach from ...

Scheme 10.9 Representative multifunctional xanthates used in RAFT polymeriza...

Scheme 10.10 Modification of the xanthate group: a summary.

Scheme 10.11 RAFT/MADIX polymerization of PNVP and end‐group transformation....

Scheme 10.12 Mechanism of the reaction by NaN

3

via a nucleophilic process....

Scheme 10.13 Modification of PNVP xanthate chain ends into hydroxyl and alde...

Scheme 10.14 A possible mechanism for the ozonolysis of xanthate.

Scheme 10.15 The mechanism for RAFT end‐groupremoval by H

2

O

2

.

Scheme 10.16 Thermolysis of PSt with

O

‐isobutyl xanthate end‐group.

Scheme 10.17 (A) RAFT synthesis of N

3

‐PVAc and

ω

‐xanthate group removal...

Chapter 11

Figure 11.1 (a) Effect of Z′Z″NC(S)‐group and (b) R group on activity of di...

Figure 11.2 RAFT polymerization publication rate per annum. Includes both pa...

Scheme 11.1 Major pathways in the mechanism of RAFT polymerization with dith...

Figure 11.3 Structural features of dithiocarbamate RAFT agents and the inter...

Scheme 11.2 Preparation of RAFT agents using carbodithioate salts.

Scheme 11.3 Preparation of dithiocarbamates from 1,1′‐thiocarbonyl diimidazo...

Scheme 11.4 Synthesis of a tertiary RAFT agent from a thiuram disulfide.

Scheme 11.5 Synthesis of a PMMA macroRAFT agent (

35

) from radical polymeriza...

Scheme 11.6 Synthesis of tertiary carboxyl‐functional dithiocarbamates via t...

Scheme 11.7 Synthesis of dithiocarbamate

54

from

14

by methylation and ion e...

Figure 11.4 Canonical forms of dithiocarbamates.

Figure 11.5 Further examples of RAFT agents with balanced activity.

Figure 11.6 Canonical forms of

N

‐(4‐pyridinyl)‐

N

‐methyldithiocarbamate switc...

Figure 11.7 Values of Δ

H

frag

, Δ

H

stab

, an...

Scheme 11.8 End‐group transformation by copper‐promoted...

Chapter 12

Figure 12.1 Representative chromophores used in light‐regulated polymerizati...

Scheme 12.1 Photomediated controlled/radical polymerization (photo‐CRP). (a)...

Figure 12.2 Absorption profiles of different RAFT agents in the visible spec...

Figure 12.3 UV–vis experiment for degradation of thiocarbonylthio compounds ...

Figure 12.4 Structures of some visible light catalyst‐free photoiniferter RA...

Scheme 12.2 Proposed mechanisms for photoinduced electron/energy transfer–re...

Scheme 12.3 Proposed mechanism for ZnTPP‐mediated PET–RAFT polymerization in...

Figure 12.5 Gas‐controlled temporal control of ZnOETPP‐mediated PET–RAFT pol...

Figure 12.6 (a) Scheme depicting layered photocatalysts in the order (top to...

Scheme 12.4 (a) Proposed mechanism of oxygen‐tolerant PET–RAFT polymerizatio...

Figure 12.7 pH‐controlled temporal control of

tetrabrominated benzoic fluore

...

Figure 12.8 Synthetic strategy for the preparation of sequence‐defined trime...

Scheme 12.5 Selective photoactivation of thiocarbonylthio compounds with SUM...

Figure 12.9 Representation showing the ZnTPP polymerization mechanism and RA...

Figure 12.10 Heat map of MICs for all polymerssynthesized in this study wher...

Figure 12.11 Schematic showing the HTP RAFT synthesis of amine‐containing an...

Figure 12.12 Polymer network structure from PRCG via photoredox catalysis us...

Figure 12.13 PET–RAFT mediated polymerization initiated from the surface of ...

Chapter 13

Scheme 13.1 Redox couples employed to initiate RAFT polymerizations at room ...

Figure 13.1 GPC traces of (a) PAM synthesized via redox‐initiated RAFT/MADIX...

Figure 13.2 (a) Schematic of a Fenton–RAFT without traditional degassing: fi...

Figure 13.3 (A) Mechanism of semi‐bio‐Fenton RAFT polymerization. (B) (a) Se...

Scheme 13.2 Mechanism of (a) ATRP with dithiocarbamates as alkyl pseudohalid...

Figure 13.4 GPC traces of PMMA‐S‐C(S)‐Ph macroinitiators (broken lines) and ...

Figure 13.5 (a) Semi‐logarithmic kinetic plots and (b) MW and dispersity evo...

Scheme 13.3 Proposed mechanism of DET−RAFT polymerization using a dithiobenz...

Figure 13.6 Molecular structures of electrochemically characterized RAFT age...

Figure 13.7 Cyclic voltammetry of 2 × 10

−3

 M DB‐3

CN,A

in DMF + 0.1 M E...

Scheme 13.4 Envisioned mechanisms of electrochemically mediated RAFT polymer...

Scheme 13.5 Reduction potential rangeof typical RAFT agents, monomers, and p...

Figure 13.8 (a) CV of 4.7 × 10

−3

 M Cu

II

(DC)

2

/bpy in the absence and pr...

Figure 13.9 Chain extension from PMMA macroinitiators via (a)

e

ATRP of BMA. ...

Figure 13.10 Temporal control in dual concurrent

e

ATRP/RAFT polymerization o...

Figure 13.11 (a) Mechanism of

e

RAFT via electro‐reduction of the diazonium s...

Chapter 14

Scheme 14.1 The generally accepted RAFT polymerization mechanism.

Figure 14.1 Common CTAs utilized to enable the synthesis of well‐defined pol...

Figure 14.2 Pseudo‐first‐order rate plots for the hydrolysis of (a) CTP, (b)...

Figure 14.3 Fraction of CTP remaining in solution over time under conditions...

Figure 14.4 (a) Polymerization kinetics for V‐501‐initiated polymerization a...

Figure 14.5 (a) Initiator‐free photopolymerizations where initiation occurs ...

Figure 14.6 Photo‐induced electron transfer RAFT polymerization using a phot...

Figure 14.7 Kinetics of 2 M HEA polymerizations in 20% methanol/PBS degassed...

Figure 14.8 (a) Pseudo‐first‐order kinetics, (b) dependence of molecular wei...

Figure 14.9 (a) Plot of monomer conversion over polymerization time, (b) pse...

Figure 14.10 HPMA polymerization kinetics obtained for the targeted poly(GMA

Figure 14.11 Phase diagram for poly(GMA

78

‐

b

‐HPMA

X

) copolymers synthesized vi...

Figure 14.12 Phase diagram summarizing the various morphologies observed for...

Scheme 14.2 R‐group (a) and Z‐group (b) strategies for preparing polymer–pro...

Chapter 15

Figure 15.1 RAFT‐mediated polymerization‐induced self‐assembly and illustrat...

Figure 15.2 Polymerization‐induced cooperative assembly (PICA). CTA stands f...

Figure 15.3 Polymerization‐induced electrostatic self‐assembly (PIESA).

Figure 15.4 Incorporation of disulfide functionality into PGMA‐

b

‐PHPMA worm ...

Figure 15.5 Phase diagram constructed for a series of PDMAAm‐

b

‐PDMAAm dibloc...

Figure 15.6 A(B)

2

star architecture promoting the formation of complex morph...

Figure 15.7 Using bis‐urea functional macroRAFT agent for ‘templated PISA’ i...

Chapter 16

Figure 16.1 General chemical structure of the four main classes of RAFT agen...

Scheme 16.1 The RAFT process operating in the main equilibrium stage highlig...

Scheme 16.2 RAFT polymerization highlighting the presence of functionality a...

Figure 16.2 Chemical structures of (a)

2‐cyano‐5‐hydroxypentan‐2‐yl benzodit

...

Scheme 16.3 The regioselective Cu(I)‐catalyzed reaction of an azide with an ...

Figure 16.3 Representative examples of RAFT CTAs in which the R‐group fragme...

Figure 16.4 The synthesis of triazole functional RAFT agents from precursor ...

Figure 16.5 Chemical structures of norbornenyl‐functional RAFT agents.

Scheme 16.4 The synthesis of α,ω‐end‐functionalized poly(

N

‐isopropylacrylami...

Scheme 16.5 The synthesis of cyclic polystyrene via intramolecular disulfide...

Scheme 16.6 Conjugation of the parathyroid peptide hormone at the...

Figure 16.6 General approaches for the desulfurization of RAFT thiocarbonylt...

Scheme 16.7 Desulfurization pathways in poly(methyl methacrylate) prep...

Scheme 16.8 General mechanism for the radical‐mediated reduction of a RAFT t...

Scheme 16.9 UV‐initiated photolysis, followed by H abstraction from EPHP as ...

Scheme 16.10 Desulfurization of RAFT‐prepared polymer via the reaction with ...

Scheme 16.11 Conversion of a nitroxide end‐terminated polystyrene to a dithi...

Scheme 16.12 Formation of hydroxy‐terminated poly(methyl methacrylate).

Scheme 16.13 The hetero Diels–Alder reaction between a diene and dithioester...

Figure 16.7 Chemical structures of benzyl (diethoxyphosphoryl)methanedithioa...

Scheme 16.14 A modular approach to AB diblock copolymers of styrene with pol...

Scheme 16.15 Synthesis of 2‐, 3‐, and 4‐arm star polymers via convergent HDA...

Scheme 16.16 The triazolinedione‐diene normal DA reaction (a) and the triazo...

Figure 16.8 Chemical structure of a urazole‐functional trithiocarbonate: but...

Scheme 16.17 Synthesis of α‐end‐functionalized poly(

n

‐butyl acrylate) by oxi...

Figure 16.9 Thiol‐X reactions potentially suitable for the modification of m...

Scheme 16.18 Nucleophilic cleavage of RAFT thiocarbonylthio end gro...

Scheme 16.19 General mechanism of the radical‐mediated double hydrothiolatio...

Scheme 16.20 Sequential HDA and thiol–yne reactions as a route to ω‐function...

Figure 16.10 The general mechanism of the base‐catalyzed thiol‐Michael react...

Scheme 16.21 Sequential end group cleavage/Michael addition with p...

Figure 16.11 Structures of poly(

N

‐isopropylacrylamide)s formed by sequential...

Scheme 16.22 Synthesis of alkyne‐functionalized cyclic polystyrene via an in...

Scheme 16.23 (a) General scheme for the preparation of thiocarbamate end‐fun...

Scheme 16.24 The synthesis of α,ω‐pyrene difunctionalized poly(

N

‐isopropylac...

Figure 16.12 Chemical structure of ({4‐cyano‐4‐[(phenylcarbonothioyl)thio]pe...

Figure 16.13 Barbiturate‐linked poly(

n

‐butyl acrylate) (a) and brom...

Figure 16.14 Chemical structure of an α‐yne/bromide‐functional polystyrene....

Figure 16.15 Chemical structures of barbiturate and imidazolium end‐function...

Scheme 16.25 Preparation of polystyrene macromonomers via a combination of S...

Scheme 16.26 Synthesis of ABA triblock copolymers of acrylic acid and acryla...

Scheme 16.27 The general thiol–pyridyl disulfide (a) and thiol–methanethiosu...

Scheme 16.28 The synthesis of an H

2

S‐releasing polymer via sequential modifi...

Figure 16.16 Chemical structures of a pentafluorophenylester‐functional R‐gr...

Scheme 16.29 End group modification via aminolysis/sulfur exchange with a pr...

Scheme 16.30 Synthesis of a squaric ester R‐group‐functional trithiocarbonat...

Scheme 16.31 Single styrene monomer insertion in a poly(methyl methacrylate)...

Scheme 16.32 Proposed mechanism for the ozonolysis of xanthates.

Chapter 17

Scheme 17.1 Reaction scheme for the addition of xanthates to less‐activated ...

Scheme 17.2 Example of a more complex SUMI for the synthesis of dithiobenzoa...

Figure 17.1 Online

1

H‐NMR monitoring of dithiobenzoate species as a function...

Scheme 17.3 Schematic representation of the single‐unit monomer insertion (S...

Figure 17.2 Recycling SEC trace recorded during consecutive purification cyc...

Figure 17.3 Flash column chromatography purification of the oligomer chain e...

Scheme 17.4 Schematic representation of a template‐assisted selective monome...

Scheme 17.5 Schematic representation of the iterative cyclization and the mo...

Scheme 17.6 Schematic representation of the SUMI process via bulky and conve...

Figure 17.4 GPC traces for the products from sequential PET‐RAFT‐SUMI into

4

...

Scheme 17.7 Mechanism of photoRAFT‐SUMI with a trithiocarbonate RAFT agent....

Scheme 17.8 Schematic representation for the synthesis of discrete pentamers...

Scheme 17.9 Schematic representation for the PET‐RAFT SUMI process for the s...

Scheme 17.10 Schematic representation of the sequence transfer strategy from...

Figure 17.5 Schematic representation of the on‐demand oligomer distributions...

Chapter 18

Scheme 18.1 Overview of the principal reactive groups suitable for post‐poly...

Scheme 18.2 Some of the most common NHS monomers.

Scheme 18.3 Most common PFP monomers and some of their derivatives.

Scheme 18.4 Some of the most common PNP monomers and their carbonate general...

Scheme 18.5 Selection of some less common activated ester monomers.

Scheme 18.6 Selection of reactive acyl, alkyl, and aryl halide monomers.

Scheme 18.7 Overview of the post‐polymerization modification available from ...

Scheme 18.8 Key aspects of the use of activated urea as protected isocyanate...

Scheme 18.9 Selection of common azlactone, anhydride, thiolactone, and disul...

Scheme 18.10 Selection of epoxide, epoxide precursor, and aziridine monomers...

Scheme 18.11 Similarities between Diels–Alder and Alder–Ene reactions.

Scheme 18.12 Overview of the carbonyl post‐polymerization modifications and ...

Scheme 18.13 Selection of CuAAC‐, SPAAC‐, SPANOC‐, and SPANC‐related structu...

Scheme 18.14 Selection of monomers for cross‐coupling and boronic acid/diol ...

Scheme 18.15 Overview of the Biginelli and the Kabachnik–Fields reactions fr...

Scheme 18.16 Selection of monomers sharing the capacity to coordinate metal ...

Scheme 18.17 The synthesis of functional block copolymer featuring PFP‐activ...

Figure 18.1 Synthetic concept of HPMA‐based copolymers derived by post‐polym...

Figure 18.2 Schematic illustration of nanogels multi‐functionalization.

Figure 18.3 Synthesis of reactive copolymers based on

N

‐vinyl lactams with p...

Figure 18.4 Strategy followed for the synthesis of sfGFP‐PEGMA bioconjugates...

Figure 18.5 Synthesis of folate‐CTA for polymerization of folate‐functionali...

Figure 18.6 Schematic for the preparation of poly(PFPA) brush via SI‐RAFT po...

Figure 18.7 (a) Synthetic scheme of silica‐supported RAFT polymerization of ...

Figure 18.8 (a) Scheme showing the ring opening of azlactone groups in the P...

Figure 18.9 Schematic representation of the immobilization of polymers onto ...

Chapter 19

Figure 19.1 Schematic representation of synthesis of polymer networks by RP,...

Figure 19.2 Chemical structure representation of a thiocarbonylthio RAFT age...

Figure 19.3 Schematic representation of multistep polymerizations including ...

Figure 19.4 Schematic representation of the synthesis of a RAFT macro‐contro...

Figure 19.5 Chemical structure representation of different bifunctional RAFT...

Figure 19.6 Schematic representation of a pressure (P) vs. temperature (T) c...

Figure 19.7 Image of a poly(HEMA‐

co

‐EGDMA) polymer network synthesized in sc...

Figure 19.8 Hildebrand solubility parameter for CO

2

around subcritical and s...

Figure 19.9 Calculated values of

χ

between a polymer network based on H...

Figure 19.10 Calculated values of

χ

between HEMA and CO

2

.

Figure 19.11 SEM images of poly(HEMA‐

co

‐EGDMA) synthesized by RAFT copolymer...

Figure 19.12 Comparison of textural characteristics of poly(HEMA‐

co

‐EGDMA) s...

Figure 19.13 Vitamin B

12

release profiles, morphology, and interpretation of...

Figure 19.14 Crosslinking reaction, where

is the crosslinking kinetic rate...

Figure 19.15 Schematic representation of the trifunctional polymer molecule ...

Figure 19.16 GPC traces of samples collected at different conversions for th...

Figure 19.17 Evolution of weight fraction of polymers containing

i

‐primary c...

Figure 19.18 Schematic representation of the multifunctional polymer molecul...

Figure 19.19 Effect of crosslinker content on (a) conversion vs. time, (b) m...

Figure 19.20 Comparison of conventional homopolymerization of styrene (Case ...

Figure 19.21 Effect of concentration of the RAFT agent on polymerization rat...

Figure 19.22 Comparison of calculated and experimental profiles of conversio...

Chapter 20

Figure 20.1 Schematic of the various architectures described in this chapter...

Figure 20.2 (a) Preparation of block copolymers by sequential RAFT polymeriz...

Figure 20.3 General chemical structures of some of the most commonly used RA...

Figure 20.4 (a) Scheme outlining the structure of difunctional CTAs linked b...

Figure 20.5 (A) Scheme showing chain extension of a multifunctional polymeri...

Figure 20.6 (a) Monomers that fall under the categories of MAMs and LAMs. Bl...

Figure 20.7 Potential polymeric structures formed during a standard RAFT dib...

Figure 20.8 Scheme showing the preparation of a macroRAFT agent and subseque...

Figure 20.9 A selection of reported ‘click’ reactions for preparation of RAF...

Figure 20.10 Copolymerization of two monomers of differing reactivity ratio ...

Scheme 20.1 Examples of core molecules carrying different CTAs as basis for ...

Figure 20.11 Schematic representation of R and Z‐group approach in the synth...

Figure 20.12 Star polymer synthesis by chain extension using a multifunction...

Figure 20.13 Methods to produce miktoarm star copolymer using RAFT polymeriz...

Figure 20.14 Three synthetic pathways used for bottlebrush polymer synthesis...

Figure 20.15 Comparison of the grafting from R‐ and Z‐group approaches. (a) ...

Figure 20.16 Positioning of the thiocarbonylthio group in a polymeric archit...

Chapter 21

Figure 21.1 An illustration of potential star polymer structures including s...

Figure 21.2 Synthesis of hyperbranched cores using a styryl‐RAFT monomer (

M

1

Figure 21.3 RAFT polymerization of star polymers using the core‐first R‐ and...

Figure 21.4 RAFT polymerization of star polymers using the Z‐group core‐firs...

Figure 21.5 RAFT polymerization of star polymers using the R‐group core‐firs...

Figure 21.6 Synthesis of star polymers via R‐group core‐first approach using...

Figure 21.7 Synthesis of star polymers using the arm‐first approach via RAFT...

Figure 21.8 (a) Synthesis of star polymers with varying arm compositions and...

Figure 21.9 Core‐crosslinked stars synthesized using emulsion and dispersion...

Figure 21.10 Photo‐mediated RAFT polymerization for the synthesis of star po...

Figure 21.11 (a) Synthesis of homopolymer and mikto‐arm star polymers via hi...

Figure 21.12 The grafting‐to approach requires the conjugation of arms with ...

Figure 21.13 Schematic illustration of the synthesis of multifunctional core...

Figure 21.14 Confocal images of water/toluene (60/40 v/v%) emulsions contain...

Figure 21.15 High internal phase emulsion (HIPE) stabilized by poly(MEA

x

‐

co

‐...

Figure 21.16 Star polymers with POSS core and hydrophilic arms stabilized MW...

Figure 21.17 Star polymers with degradable inner block and crosslinkable she...

Chapter 22

Figure 22.1 Brush regimes on flat surfaces (a); Brush conformations on curve...

Scheme 22.1 Common polymer grafting strategies: (a) physisorption, (b) graft...

Figure 22.2 RAFT attachment strategies: (a) surface‐tethered radical initiat...

Figure 22.3 Some complex brush architectures prepared via SI‐RAFT: (a) bimod...

Scheme 22.2 Synthetic strategy to prepare bimodal brush‐grafted silica nanop...

Scheme 22.3 Proposed mechanism for the formation of polymer loops via doubly...

Figure 22.4 (a) Synthetic route to prepare small (15 nm diameter) Janus nano...

Figure 22.5 Scanning electron microscopy (SEM) images of styrene latex parti...

Figure 22.6 Illustration of CTA photopatterning via a light‐activated photoe...

Figure 22.7 (a) Pseudo‐first‐order kinetics plot showing each on‐and‐off cyc...

Figure 22.8 Cell sheets recovered from grafted PNIPAM brush surfaces by redu...

Figure 22.9 Proposed mechanism for dually responsive DOX release from PMAA‐

b

Figure 22.10 Experimentally determined morphology diagram of PS‐

g

‐SiO

2

in th...

Figure 22.11 (a) First‐order kinetic plots and (b) dependence of molecular w...

Figure 22.12 TEM images of LLDPE nanocomposites each filled with 4 wt% silic...

Figure 22.13 (a) Computer‐simulated ‘heatmap’ of monomer density in NPs (dia...

Figure 22.14 (a) 20 wt% PMMA‐

g

‐SiO

2

in 100 kg mol

−1

PEO quenched at ro...

Figure 22.15 Illustrations of PGNP preparation of various structures by ‘ass...

Figure 22.16 PISA synthesis of PGlyMA‐

b

‐PHPMA diblock copolymer worms and il...

Chapter 23

Figure 23.1 (a) Relationship between acid strength or concentration on the p...

Figure 23.2 Schematic representation of acid/base switchable RAFT agents for...

Figure 23.3 Schematic representation of the system for the self‐optimization...

Figure 23.4 Schematic representation of the automated parallel synthesis of ...

Figure 23.5 Schematic representation of enzymatically degassed photo‐PISA‐RA...

Figure 23.6 Graphic representation of the macromolecular characteristics of ...

Figure 23.7 Design of polymer carriers to tailor solubilization for highly h...

Figure 23.8 Schematic representation of a HT/HO‐E workflow for the discovery...

Figure 23.9 Images of commercially available HO‐E tools for photo‐assisted p...

Chapter 24

Figure 24.1 Structural features of macromonomer RAFT agents and the intermed...

Figure 24.2 Number of patents or patent applications issued per year on thio...

Chapter 25

Figure 25.1 Three general mechanisms for living cationic polymerization. (a)...

Figure 25.2 General scheme for cationic RAFT polymerization using RSC(S)Z an...

Figure 25.3 Intermediates in cationic RAFT or DT polymerization.

Figure 25.4 Various cationic RAFT or DT agents.

Figure 25.5 Initiators, cationogens, and catalysts for cationic RAFT or DT p...

Figure 25.6 Monomers for cationic RAFT or DT polymerization.

Figure 25.7 End‐functionalized polymers via cationic RAFT or DT polymerizati...

Figure 25.8 Block copolymers via cationic RAFT or DT polymerization.

Figure 25.9 Star polymers via cationic RAFT or DT polymerization.

Guide

Cover

Table of Contents

Title Page

Title Page

Copyright

Preface

Acknowledgements

Begin Reading

Index

End User License Agreement

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RAFT Polymerization

Methods, Synthesis and Applications

Volume 1

Edited by

Graeme Moad

Ezio Rizzardo

RAFT Polymerization

Methods, Synthesis and Applications

Volume 2

Edited by

Graeme Moad

Ezio Rizzardo

Editors

Prof. Dr. Graeme Moad

CSIRO Manufacturing

Research Way

Clayton, Victoria 3168

Australia

Dr. Ezio Rizzardo

CSIRO Manufacturing

Research Way

Clayton, Victoria 3168

Australia

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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