Sustainable Polymers from Biomass

List of Contributors xi

1 Introduction 1
Mitra S. Ganewatta, Chuanbing Tang, and Chang Y. Ryu

1.1 Introduction 1

1.2 Sustainable Polymers 2

1.3 Biomass Resources for Sustainable Polymers 4

1.4 Conclusions 8

References 8

2 Polyhydroxyalkanoates: Sustainability, Production, and Industrialization 11
Ying Wang and Guo-Qiang Chen

2.1 Introduction 11

2.2 PHA Diversity and Properties 14

2.3 PHA Production from Biomass 16

2.4 PHA Application and Industrialization 26

2.5 Conclusion 28

Acknowledgment 28

References 28

3 Polylactide: Fabrication of Long Chain Branched Polylactides and Their Properties and Applications 35
Zhigang Wang and Huagao Fang

3.1 Introduction 35

3.2 Fabrication of LCB PLAs 36

3.3 Structural Characterization on LCB PLAs 38

3.4 The Rheological Properties of LCB PLAs 43

3.5 Crystallization Kinetics of LCB PLAs 46

3.6 Applications of LCB PLAs 48

3.7 Conclusions 51

Acknowledgments 51

References 51

4 Sustainable Vinyl Polymers via Controlled Polymerization of Terpenes 55
Masami Kamigaito and Kotaro Satoh

4.1 Introduction 55

4.2 β-Pinene 57

4.3 α-Pinene 63

4.4 Limonene 65

4.5 β-Myrcene, α-Ocimene, and Alloocimene 69

4.6 Other Terpene or Terpenoid Monomers 76

4.7 Conclusion 80

Abbreviations 80

References 81

5 Use of Rosin and Turpentine as Feedstocks for the Preparation of Polyurethane Polymers 91
Meng Zhang, Yonghong Zhou, and Jinwen Zhang

5.1 Introduction 91

5.2 Rosin Based Polyurethane Foams 92

5.3 Rosin-Based Polyurethane Elastomers 95

5.4 Terpene-Based Polyurethanes 95

5.5 Terpene-Based Waterborne Polyurethanes 97

5.6 Rosin-Based Shape Memory Polyurethanes 99

5.7 Conclusions 100

References 101

6 Rosin-Derived Monomers and Their Progress in Polymer Application 103
Jifu Wang, Shaofeng Liu, Juan Yu, Chuanwei Lu, Chunpeng Wang, and Fuxiang Chu

6.1 Introduction 103

6.2 Rosin Chemical Composition 104

6.3 Rosin Derived Monomers for Main-Chain Polymers 105

6.4 Rosin-Derived Monomers for Side-Chain Polymers 112

6.5 Rosin-Derived Monomers for Three-Dimensional Rosin-Based Polymer 131

6.6 Outlook and Conclusions 140

Acknowledgments 141

References 141

7 Industrial Applications of Pine-Chemical-Based Materials 151
Lien Phun, David Snead, Phillip Hurd, and Feng Jing

7.1 Pine Chemicals Introduction 151

7.2 Crude Tall Oil 151

7.3 Terpenes 153

7.4 Tall Oil Fatty Acid 159

7.5 Rosin 167

7.6 Miscellaneous Products 173

References 178

8 Preparation and Applications of Polymers with Pendant Fatty Chains from Plant Oils 181
Liang Yuan, Zhongkai Wang, Nathan M. Trenor, and Chuanbing Tang

8.1 Introduction 181

8.2 (Meth)acrylate Monomers Preparation and Polymerization 182

8.3 Norbornene Monomers and Polymers for Ring Opening Metathesis Polymerization (ROMP) 194

8.4 2-Oxazoline Monomers for Living Cationic Ring Opening Polymerization 195

8.5 Vinyl Ether Monomers for Cationic Polymerization 200

8.6 Conclusions and Outlook 203

References 204

9 Structure–Property Relationships of Epoxy Thermoset Networks from Photoinitiated Cationic Polymerization of Epoxidized Vegetable Oils 209
Zheqin Yang, Jananee Narayanan, Matthew Ravalli, Brittany T. Rupp, and Chang Y. Ryu

9.1 Introduction 209

9.2 Photoinitiated Cationic Polymerization of Epoxidized Vegetable Oils 213

9.3 Conclusions 224

Acknowledgment 225

References 225

10 Biopolymers from Sugarcane and Soybean Lignocellulosic Biomass 227
Delia R. Tapia-Blácido, Bianca C. Maniglia, and Milena Martelli-Tosi

10.1 Introduction 227

10.2 Lignocellulosic Biomass Composition and Pretreatment 229

10.3 Lignocellulosic Biomass from Soybean 233

10.4 Production of Polymers from Soybean Biomass 234

10.5 Lignocellulosic Biomass from Sugarcane 242

10.6 Production of Polymers from Sugarcane Bagasse 242

10.7 Conclusion and Future Outlook 246

Acknowledgments 247

References 247

11 Modification of Wheat Gluten-Based Polymer Materials by Molecular Biomass 255
Xiaoqing Zhang

11.1 Introduction 255

11.2 Modification of Wheat Gluten Materials by Molecular Biomass 257

11.3 Biodegradation of Wheat Gluten Materials Modified by Biomass 269

11.4 Biomass Fillers for WG Biocomposites 271

11.5 Conclusion and Future Perspectives of WG-Based Materials 272

References 273

12 Copolymerization of C1 Building Blocks with Epoxides 279
Ying-Ying Zhang and Xing-Hong Zhang

12.1 Introduction 279

12.2 CO2/Epoxide Copolymerization 280

12.3 CS2/Epoxide Copolymerization 295

12.4 COS/Epoxide Copolymerization 299

12.5 Properties of C1-Based Polymers 304

12.6 Conclusions and Outlook 307

References 307

13 Double-Metal Cyanide Catalyst Design in CO2/Epoxide Copolymerization 315
Joby Sebastian and Darbha Srinivas

13.1 Introduction 315

13.2 Polycarbonates and Their Synthesis Methods 317

13.3 Copolymerization of CO2 and Epoxides 318

13.4 Double-Metal Cyanides and Their Structural Variation 319

13.5 Methods of DMC Synthesis 322

13.6 Factors Influencing Catalytic Activity of DMCs 323

13.7 Role of Co-catalyst on the Activity of DMC Catalysts 332

13.8 Copolymerization in the Presence of Hybrid DMC Catalysts 334

13.9 Copolymerization with Nano-lamellar DMC Catalysts 335

13.10 Effect of Crystallinity and Crystal Structure of DMC on Copolymerization 337

13.11 Effect of Method of Preparation of DMC Catalysts on Their Structure and Copolymerization Activity 337

13.12 Reaction Mechanism of Copolymerization 340

13.13 Conclusions 342

References 343

Index 347

Chuanbing Tang is Associate Professor and College of Arts and Sciences Distinguished Professor in the Department of Chemistry and Biochemistry at the University of South Carolina. He received his B.S. degree in Polymer Science from Nanjing University and Ph.D. in Chemistry from Carnegie Mellon University under the direction of Krzysztof Matyjaszewski and Tomasz Kowalewski. He was also a postdoctoral researcher with Craig Hawker and Edward Kramer at the University of California at Santa Barbara. His research interests include organic polymer synthesis, sustainable polymers from renewable natural resources, metal-containing polymers, and polymers for biomedical application. He has been recognized with a few awards including South Carolina Governor?s Young Scientist Award, NSF Career Award, Thieme Chemistry Journal Award and USC Distinguished Undergraduate Research Mentor Award. He has also been named a Breakthrough Rising Star at the University of South Carolina and an ACS PMSE Young Investigator. He has published over 100 papers and 10 patents.

Chang Y. Ryu is Professor of Chemistry and Chemical Biology and Director of New York State Center for Polymer Synthesis at Rensselaer Polytechnic Institute (RPI). He completed his B.S. and M.S. in Chemical Technology at Seoul National University and received his Ph.D. in Chemical Engineering at the University of Minnesota under the direction of Tim Lodge. He served as a postdoctoral researcher with Ed Kramer and Glenn Fredrickson in the Materials Research Laboratory at the University of California at Santa Barbara and started his faculty position at RPI in 2000. He has been awarded the IUPAC Young Observer Award (2007), NSF CAREER Award (2005), and the Arthur K. Doolittle Award from the ACS Division of Polymeric Materials Science and Engineering (1998). His research focuses on macromolecular separation and adsorption, block copolymer self-assembly, and photopolymerization as well as structure-property-