Accounts on Sustainable Flow Chemistry (eBook)

Contents 6
Preface 7
Solar Photochemistry in Flow 9
Abstract 9
1 Introduction 10
2 Historical Perspective 10
3 Solar Radiation 11
3.1 Solar Constant 11
3.2 Spectral Distribution of the Extraterrestrial Solar Irradiance 11
3.3 Spectral Distribution of the Ground Solar Irradiance 12
3.4 Diffuse Solar Radiation 15
3.5 Solar Productivity Metrics 16
4 Reactor Designs 17
4.1 Solfin 17
4.2 SOLARIS and PROPHIS 21
4.3 MPI Line-focusing Reactor 24
4.4 Sunflow and Similar Design 26
4.5 Compound Parabolic Concentrator-based Reactors (CPC) 28
4.6 Luminescent solar concentrator-photomicroreactor (LSC-PM) 29
4.7 Outlook 32
Acknowledgements 33
References 33
Supported Catalysts for Continuous Flow Synthesis 36
Abstract 36
1 Introduction 36
2 Heterogenous Catalysis in Flow 37
3 Use of Supported Organocatalysts in Heterogeneous Flow Catalysis 38
4 Use of Supported CatalystsReagents in Continuous-Flow Kinetic Resolutions 53
5 Use of Supported Organometallic Catalysts in Heterogeneous Flow Catalysis 54
6 Use of Wall-Coated Approaches in Heterogeneous Flow Catalysis 66
7 Conclusions 68
References 70
The Use of Molecular Oxygen for Liquid Phase Aerobic Oxidations in Continuous Flow 73
Abstract 73
1 Introduction 74
2 Process Aspects 76
2.1 Mass and Heat Transfer 76
2.2 Technology 77
2.3 Using Diluted O2 78
2.4 Ability to Use Pure O2 79
2.5 Scale-up and Manufacture 80
3 Homogeneous Catalysis 81
3.1 Pd-Catalyzed Reactions 81
3.2 Cu-Catalyzed Reactions 84
3.3 Miscellaneous 85
4 Heterogeneous Catalysis 87
5 Uncatalyzed Reactions 92
6 Organomagnesium and Organolithium Reagents 94
7 Membrane Technologies 95
7.1 Tube-in-Tube Reactor 96
7.2 Tube-in-Shell Reactor 99
7.3 Dual- and Triple- Channel Microreactor 99
8 Photochemistry and Singlet Oxygen 100
9 Electrochemistry 102
10 Green Solvents 103
10.1 Carbon Dioxide 104
10.2 Water 106
11 Novel Reactor Developments 107
12 Conclusion 109
Acknowledgements 110
References 110
Sustaining the Transition from a Petrobased to a Biobased Chemical Industry with Flow Chemistry 117
Abstract 117
1 Introduction 118
2 Commodity and Other Large-Scale Industrially Relevant Building Blocks 119
2.1 Solvents 119
2.1.1 Alkanes 119
2.1.2 Alcohols 120
2.1.3 Ethers 121
2.1.4 Lactones 123
2.1.5 Cyclic Carbonates 124
2.1.6 Aromatics 125
2.2 Monomers 125
2.2.1 Olefins 125
2.2.2 Diols 129
2.2.3 Lactide 131
2.2.4 FDCA 132
2.3 Other Important Olefinic Building Blocks 133
3 Specialty, Fine, and Niche Chemicals 134
3.1 Specialty Monomers 134
3.2 Building Blocks for the Agrochemical and Pharmaceutical Industries 135
3.2.1 Carbonyls 135
3.2.2 N-Heterocycles 136
3.2.3 O-Heterocycles 138
3.3 Other High Value-Added Targets 139
4 Fuels and Additives 140
4.1 Derivatives of Glycerol 140
4.2 Derivatives of Levulinic Acid 142
4.3 Derivatives of HMF and Furfural 144
5 Conclusion and Perspectives 146
Acknowledgements 146
References 146
Continuous-Flow Microreactors for Polymer Synthesis: Engineering Principles and Applications 152
Abstract 152
1 Introduction 153
2 Mass Transport Phenomena in Polymerization Processes 155
2.1 Mixing Characteristics in Homogeneous Polymerization Processes 155
2.2 Mass Transfer in Heterogeneous Polymerization Processes 162
3 Heat Transfer and Energy Dissipation in Polymerization Processes 165
4 Polymerization in Continuous-Flow Microreactors 169
4.1 Homogeneous Polymerization 169
4.1.1 Free Radical Polymerization 169
4.1.2 Living Polymerization 169
4.2 Cationic Polymerization 170
4.3 Anionic Polymerization 170
4.3.1 Controlled Radical Polymerization 171
4.4 ATRP Processes 171
4.5 RAFT Processes 172
4.6 NMP Processes 174
4.6.1 Polycondensation 174
4.7 Heterogeneous Polymerization 176
4.7.1 Free-Radical Polymerization Preparing Polymer Microspheres with Controllable Morphologies 176
4.7.2 Controlled Living Polymerization for Synthesis of Functional Polymers 178
4.7.3 Catalyzed Polymerization 180
4.7.4 Channel Clogging Issue Solved by Heterogeneous Operations 182
4.8 Photopolymerization in Microreactors 183
4.8.1 Photo-induced Radical Polymerization 184
4.8.2 PhotoRAFT Processes 186
4.8.3 Other Photopolymerization Processes in Microreactors 188
5 Challenges and Remarking Conclusions 190
Acknowledgements 191
References 191