Sustainable Polymers from Biomass

Sustainable Polymers from Biomass

Edited by Chuanbing Tang and Chang Y. Ryu

Editors

Prof. Chuanbing TangUniversity of South CarolinaDept. of Chemistry & Biochemistry631 Sumter StreetSCUnited States

Prof. Chang Y. RyuRensselaer Polytechnic InstituteDept. of Chemistry & Chemical Biology110 8th StreetNYUnited States

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v

Contents

List of Contributors xi

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

1.1 Introduction 11.2 Sustainable Polymers 21.3 Biomass Resources for Sustainable Polymers 41.3.1 Natural Biopolymers 41.3.2 Monomers and Polymers from Biomass 61.4 Conclusions 8 References 8

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

2.1 Introduction 112.2 PHA Diversity and Properties 142.2.1 PHA Diversity 142.2.2 PHA Properties 152.3 PHA Production from Biomass 162.3.1 PHA Production Strains 162.3.2 PHA Synthesis Pathways 172.3.3 PHA Production from Unrelated Carbon Sources 172.3.3.1 Production of P3HB4HB from Unrelated Carbon Sources 192.3.3.2 PHBV Production from Various Substrates 242.3.3.3 PHA Production Under Seawater-Based Open and Continuous

Conditions from Mixed Substrates 252.4 PHA Application and Industrialization 262.5 Conclusion 28 Acknowledgment 28 References 28

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

3.1 Introduction 35

Contentsvi

3.2 Fabrication of LCB PLAs 363.2.1 LCB PLAs on the Basis of the Group Reaction Mechanism 363.2.2 LCB PLAs on the Bases of the Radical Coupling Mechanism 373.3 Structural Characterization on LCB PLAs 383.3.1 Size-Exclusion Chromatography (SEC) 393.3.2 Rheology 403.4 The Rheological Properties of LCB PLAs 433.5 Crystallization Kinetics of LCB PLAs 463.6 Applications of LCB PLAs 483.7 Conclusions 51 Acknowledgments 51 References 51

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

4.1 Introduction 554.2 β-Pinene 574.2.1 Cationic Polymerization 574.2.2 Radical Copolymerization 604.2.3 Polymerization of β-Pinene-Derived Vinyl Monomers 624.3 α-Pinene 634.3.1 Cationic Polymerization 634.3.2 Polymerization of α-Pinene-Derived Vinyl Monomers 644.4 Limonene 654.4.1 Cationic Polymerization 654.4.2 Radical Copolymerization 654.4.3 Coordination Polymerization and ROMP 684.5 β-Myrcene, α-Ocimene, and Alloocimene 694.5.1 Radical Polymerization 694.5.2 Cationic Polymerization 714.5.3 Anionic Polymerization 734.5.4 Coordination Polymerization 744.5.5 Polymerization of Myrcene-Derived Vinyl Monomers 764.6 Other Terpene or Terpenoid Monomers 764.6.1 α- and β-Phellandrenes 764.6.2 β-Farnesene 774.6.3 β-Caryophyllene and α-Humulene 784.6.4 Monoterpene Aldehydes 784.7 Conclusion 80 Abbreviations 80 References 81

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

5.1 Introduction 91

Contents vii

5.2 Rosin Based Polyurethane Foams 925.3 Rosin-Based Polyurethane Elastomers 955.4 Terpene-Based Polyurethanes 955.5 Terpene-Based Waterborne Polyurethanes 975.6 Rosin-Based Shape Memory Polyurethanes 995.7 Conclusions 100 References 101

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

6.1 Introduction 1036.2 Rosin Chemical Composition 1046.3 Rosin Derived Monomers for Main-Chain Polymers 1056.3.1 Rosin-Derived Main-Chain Polymers from MPA and its

Derivatives 1056.3.2 Rosin-Derived Polymers from APA and its Derivatives 1076.3.3 Ketonic Type Rosin-Derived Macro-Monomers 1106.3.4 Others 1116.4 Rosin-Derived Monomers for Side-Chain Polymers 1126.4.1 Rosin Derived Monomers 1126.4.2 Side-Chain Linear Homopolymers 1146.4.2.1 Side-Chain Linear Homopolymers Prepared by ATRP 1146.4.2.2 Side-Chain Linear Homopolymer Prepared by RAFT 1156.4.3 Side-Chain Linear Copolymers 1166.4.3.1 Side-Chain Linear Rosin Acid-Caprolactone Block Copolymers 1166.4.3.2 Side-Chain Linear Rosin Acid-PEG Amphiphilic Block

Copolymers 1186.4.4 Side-Chain Grafted Copolymers 1206.4.4.1 Side-Chain Grafted Copolymer by Click Chemistry 1206.4.4.2 Side-Chain Grafted Copolymer by ATRP 1246.4.4.3 Side-Chain Grafted Copolymer by Other Method 1306.5 Rosin-Derived Monomers for Three-Dimensional Rosin-Based

Polymer 1316.5.1 Three-Dimensional Rosin-based Polymer by Condensation

Polymerization 1326.5.1.1 Rosin Modified Phenolic Resins 1326.5.1.2 Rosin-based Polyurethane 1336.5.1.3 Rosin-based Thermoset Resin from Epoxy Resin 1346.5.2 Three-Dimensional Rosin-based Polymer by Free Radical

Polymerization 1366.5.2.1 Rosin-based UV Curing Resin 1366.5.2.2 Rosin-based Thermal Curing Resin 1386.6 Outlook and Conclusions 140 Acknowledgments 141 References 141

Contentsviii

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

7.1 Pine Chemicals Introduction 1517.2 Crude Tall Oil 1517.3 Terpenes 1537.3.1 Terpene Resins 1537.4 Tall Oil Fatty Acid 1597.4.1 TOFA-Based Alkyds 1607.4.2 TOFA for Polyamides 1607.4.3 Oxidized Tall Oil 1617.4.4 Polyurethanes 1627.4.5 Epoxy Resin Esters 1647.4.6 Amidoamine Epoxy Resins 1667.5 Rosin 1677.5.1 Adhesives-Polyesters 1687.5.2 Coatings 1697.5.3 Epoxies 1697.5.4 Modified Rosin Polymers 1707.5.5 Insulation 1707.5.6 Inks 1707.5.7 Plastics 1717.5.8 Paper Size 1727.5.9 Surfactants 1727.5.10 Other 1727.6 Miscellaneous Products 173 References 178

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

8.1 Introduction 1818.2 (Meth)acrylate Monomers Preparation and Polymerization 1828.2.1 From Fatty Acid Methyl Esters 1828.2.2 From Fatty Acids 1848.2.3 From Fatty Alcohols 1868.2.3.1 Anionic Polymerization 1868.2.3.2 Group Transfer Polymerization 1878.2.3.3 Atom Transfer Radical Polymerization (ATRP) 1878.2.3.4 Reversible Addition-Fragmentation Chain-Transfer Polymerization

(RAFT) 1918.2.4 From N-Alkylhydroxyl Amides 1918.3 Norbornene Monomers and Polymers for Ring Opening Metathesis

Polymerization (ROMP) 1948.4 2-Oxazoline Monomers for Living Cationic Ring Opening

Polymerization 1958.5 Vinyl Ether Monomers for Cationic Polymerization 200

Contents ix

8.6 Conclusions and Outlook 203 References 204

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

9.1 Introduction 2099.2 Photoinitiated Cationic Polymerization of Epoxidized Vegetable

Oils 2139.2.1 Epoxidized Vegetable Oils (EVOs) 2139.2.2 Photo-initiated Cationic Polymerization of ESO: Structure–Property

Relationship 2149.2.3 Photo-initiated Cationic Polymerization of ELO: Thickness

Control 2219.3 Conclusions 224 Acknowledgment 225 References 225

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

10.1 Introduction 22710.2 Lignocellulosic Biomass Composition and Pretreatment 22910.3 Lignocellulosic Biomass from Soybean 23310.4 Production of Polymers from Soybean Biomass 23410.5 Lignocellulosic Biomass from Sugarcane 24210.6 Production of Polymers from Sugarcane Bagasse 24210.7 Conclusion and Future Outlook 246 Acknowledgments 247 References 247

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

11.1 Introduction 25511.2 Modification of Wheat Gluten Materials by Molecular

Biomass 25711.2.1 Modification of WG by Natural Phenolics 25811.2.2 Modification by Epoxidized Vegetable Oil 26411.3 Biodegradation of Wheat Gluten Materials Modified

by Biomass 26911.4 Biomass Fillers for WG Biocomposites 27111.5 Conclusion and Future Perspectives of WG-Based Materials 272 References 273

Contentsx

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

12.1 Introduction 27912.2 CO2/Epoxide Copolymerization 28012.2.1 Heterogeneous Zn─Co(III) DMCC 28112.2.1.1 Structure of Zn─Co(III) DMCC 28212.2.1.2 CO2/Epoxide Copolymerization via Zn─Co(III) DMCC

Catalysis 28612.2.1.3 Copolymerization of CO2 with Biomass Monomers 28812.3 CS2/Epoxide Copolymerization 29512.4 COS/Epoxide Copolymerization 29912.5 Properties of C1-Based Polymers 30412.5.1 Thermal Property 30412.5.2 Mechanical Property 30612.5.3 Biodegradability 30612.5.4 Optical Property 30612.6 Conclusions and Outlook 307 References 307

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

13.1 Introduction 31513.2 Polycarbonates and Their Synthesis Methods 31713.3 Copolymerization of CO2 and Epoxides 31813.4 Double-Metal Cyanides and Their Structural Variation 31913.5 Methods of DMC Synthesis 32213.6 Factors Influencing Catalytic Activity of DMCs 32313.6.1 Hexacyanometallate 32313.6.2 Complexing Agent 32513.6.3 Co-complexing Agent 32613.6.4 Zinc Precursor/Halide Precursor 32913.6.5 Cobalt Precursor 33113.7 Role of Co-catalyst on the Activity of DMC Catalysts 33213.8 Copolymerization in the Presence of Hybrid DMC Catalysts 33413.9 Copolymerization with Nano-lamellar DMC Catalysts 33513.10 Effect of Crystallinity and Crystal Structure of DMC

on Copolymerization 33713.11 Effect of Method of Preparation of DMC Catalysts on Their Structure

and Copolymerization Activity 33713.12 Reaction Mechanism of Copolymerization 34013.12.1 Polymerization in the Presence of Initiators 34013.12.2 Polymerization in the Absence of Initiators 34113.13 Conclusions 342 References 343

Index 347

xi

Guo-Qiang ChenTsinghua-Peking Center for Life Sciences, Tsinghua UniversityCenter for Synthetic and Systems Biology, School of Life ScienceBeijing 100084P. R. China

Fuxiang ChuChinese Academy of ForestryInstitute of Chemical Industry of Forestry ProductsNanjing 210042P. R. China

Huagao FangHefei University of TechnologyDepartment of Polymer Science and Engineering, School of Chemistry and Chemical Engineering, Key Laboratory of Advanced Functional Materials and DevicesHefei, Anhui Province 230009P. R. China

Mitra S. GanewattaUniversity of South CarolinaDepartment of Chemistry and Biochemistry631 Sumter StreetColumbia, SC 29208USA

Phillip HurdGeorgia-Pacific Chemicals LLC, Technology Center2883 Miller RoadDecatur, GA 30035USA

Feng JingAlcon Laboratories, Inc.11460 Johns Creek ParkwayDuluth, GA 30097USA

Masami KamigaitoNagoya UniversityDepartment of Applied Chemistry, Graduate School of EngineeringFuro-cho, Chikusa-kuNagoya 464-8603Japan

Shaofeng LiuChinese Academy of ForestryInstitute of Chemical Industry of Forestry ProductsNanjing 210042P. R. China

Chuanwei LuChinese Academy of ForestryInstitute of Chemical Industry of Forestry ProductsNanjing 210042P. R. China

List of Contributors

fbetw.indd 11 1/19/2017 3:38:53 PM

List of Contributorsxii

Bianca C. ManigliaUniversidade de São PauloDepartamento de Química, Faculdade de Filosofia, Ciências e Letras de Ribeirão PretoRibeirão Preto, SPBrazil

Milena Martelli-TosiUniversidade de São PauloDepartamento de Química, Faculdade de Filosofia, Ciências e Letras de Ribeirão PretoRibeirão Preto, SPBrazil

Jananee NarayananDepartment of Chemistry and Chemical Biology, Rensselaer Polytechnic Institute, New York State Center for Polymer Synthesis110 8th StreetTroy, NY 12180USA

Lien PhunGeorgia-Pacific Chemicals LLC, Technology Center2883 Miller RoadDecatur, GA 30035USA

Matthew RavalliDepartment of Chemistry and Chemical Biology, Rensselaer Polytechnic Institute, New York State Center for Polymer Synthesis110 8th StreetTroy, NY 12180USA

Brittaney RuppDepartment of Chemistry and Chemical Biology, Rensselaer Polytechnic Institute, New York State Center for Polymer Synthesis110 8th StreetTroy, NY 12180USA

Chang Y. RyuDepartment of Chemistry and Chemical Biology, Rensselaer Polytechnic Institute, New York State Center for Polymer Synthesis110 8th StreetTroy, NY 12180USA

Kotaro SatohNagoya UniversityDepartment of Applied Chemistry, Graduate School of EngineeringFuro-cho, Chikusa-kuNagoya 464-8603Japan

Joby SebastianCatalysis and Inorganic Chemistry Division, CSIR-National Chemical LaboratoryDr. Homi Bhabha RoadPune 411 008India

and

India and Academy of Scientific and Innovative Research (AcSIR)New Delhi 110 001India

fbetw.indd 12 1/19/2017 3:38:53 PM

List of Contributors xiii

David SneadGeorgia-Pacific Chemicals LLC, Technology Center2883 Miller RoadDecatur, GA 30035USA

Darbha SrinivasCatalysis and Inorganic Chemistry Division, CSIR-National Chemical LaboratoryDr. Homi Bhabha RoadPune 411 008India

and

India and Academy of Scientific and Innovative Research (AcSIR)New Delhi 110 001India

Chuanbing TangUniversity of South CarolinaDepartment of Chemistry and Biochemistry631 Sumter StreetColumbia, SC 29208USA

Delia R. Tapia-BlácidoUniversidade de São PauloDepartamento de Química, Faculdade de Filosofia, Ciências e Letras de Ribeirão PretoRibeirão Preto, SPBrazil

Nathan M. TrenorUniversity of South CarolinaDepartment of Chemistry and Biochemistry631 Sumter StreetColumbia, SC 29208USA

Chunpeng WangChinese Academy of ForestryInstitute of Chemical Industry of Forestry ProductsNanjing 210042P. R. China

Jifu WangChinese Academy of ForestryInstitute of Chemical Industry of Forestry ProductsNanjing 210042P. R. China

Ying WangSchool of Life Science, Beijing Institute of TechnologyBeijing 100081P. R. China

Zhigang WangUniversity of Science and Technology of ChinaCAS Key Laboratory of Soft Matter Chemistry, Department of Polymer Science and Engineering, Hefei National Laboratory for Physical Sciences at the MicroscaleHefei, Anhui Province 230026P. R. China

Zhongkai WangUniversity of South CarolinaDepartment of Chemistry and Biochemistry631 Sumter StreetColumbia, SC 29208USA

Zheqin YangDepartment of Chemistry and Chemical Biology, Rensselaer Polytechnic Institute, New York State Center for Polymer Synthesis110 8th StreetTroy, NY 12180USA

fbetw.indd 13 1/19/2017 3:38:53 PM

List of Contributorsxiv

Juan YuChinese Academy of ForestryInstitute of Chemical Industry of Forestry ProductsNanjing 210042P. R. China

Liang YuanUniversity of South CarolinaDepartment of Chemistry and Biochemistry631 Sumter StreetColumbia, SC 29208USA

Jinwen ZhangWashington State UniversityComposite Materials and Engineering Center, School of Mechanical and Materials EngineeringPullman, WA 99163USA

Meng ZhangResearch Institute for Forestry New Technology, CAFBeijing, 100091P. R. China

and

Institute of Chemical Industry of Forestry Products, CAFNanjing 210042P. R. China

Xiaoqing ZhangCSIRO ManufacturingGate 3, Normanby RoadClayton, VIC 3168Australia

Xing-Hong ZhangZhejiang UniversityMOE Key Laboratory of Macromolecular Synthesis and Functionalization, Department of Polymer Science and EngineeringHangzhou 310027P. R. China

Ying-Ying ZhangZhejiang UniversityMOE Key Laboratory of Macromolecular Synthesis and Functionalization, Department of Polymer Science and EngineeringHangzhou 310027P. R. China

Yonghong ZhouResearch Institute for Forestry New Technology, CAFBeijing 100091P. R. China

and

Institute of Chemical Industry of Forestry Products, CAFNanjing 210042P. R. China

fbetw.indd 14 1/19/2017 3:38:53 PM

1

Sustainable Polymers from Biomass, First Edition. Edited by Chuanbing Tang and Chang Y Ryu.© 2017 Wiley-VCH Verlag GmbH & Co. KGaA. Published 2017 by Wiley-VCH Verlag GmbH & Co. KGaA.

1

1.1 Introduction

The discovery and development of synthetic polymeric materials in the twenti-eth century is undisputedly recognized as one of the most significant inventions humans have made to improve the quality of life. Durability, light weight, pro-cessability, and diverse physiochemical properties are just a few merits why poly-meric materials are widely used for the manufacture of simple water bottles to setting up modern space stations. Outstanding processability features along with adequate physical properties have resulted in polymeric materials displacing many other materials, such as wood, metal, and glass to a considerable extent. Packaging, construction, transportation, aerospace, biomedical, energy, and mil-itary are few examples of industrial sectors, where polymeric materials prevail. Global production of plastic has risen from 204 million tons in 2002 to about 299 million tons in 2013 [1]. Manufacture of non‐natural polymers is largely associ-ated with the utilization of essentially non‐renewable fossil feedstocks, either natural gas or petroleum. Approximately, 5–8% of the global oil production is used for plastic production [2]. Accompanying environmental problems include, but are not limited to, generation of solid waste that accumulates in landfills and oceans, production pollution and related environmental problems [3]. A major underlying issue in the use of plastics is the enormous carbon footprint associ-ated with their production as portrayed by burning 1 kg of plastics to generate about 3–6 kg of CO2 (including production and incineration) [2]. In addition, their impervious nature to enzymatic breakdown and “linear” consumption as opposed to natural counterparts results in relentless generation of solid waste from most commercial polymers. Although polymers can be recycled to pro-duce new materials or incinerated to recover its heating source value, such an endeavor is neither clearly understood by the majority of consumers nor techno-logical advances are available in most parts of the world. Depleting oil reserves as well as these detrimental environmental impacts observed in the twentyfirst century have driven government, academia, private sectors, and non‐profit organizations to explore sustainable polymers from renewable biomass as a long‐term alternative. In addition, the consumers’ preference as well as the gov-ernmental landscape has shaped in favor of sustainable products for a greener

IntroductionMitra S. Ganewatta, Chuanbing Tang, and Chang Y. Ryu

1 Introduction2

environment. Significant advancements have been made to discover sustainable polymers that are cost‐effective to manufacture, as well as compete or out‐per-form traditional materials in mechanical aspects as well as from environmental standpoints [4]. The valuable contributions to the field by several recent books [5, 6] and reviews [7–11] broadly discuss about sustainable polymeric materials. Our objective is to provide a perspective of the efforts to convert small molecu-lar biomass into sustainable polymers in different continents. This introductory chapter overviews sustainable polymers in general and briefly summarizes the content of each chapter afterward.

1.2 Sustainable Polymers

Given the influence of polymers as an indispensable resource for the modern society, it should be taken as a firm concern for sustainable development. There are many statements to define the term of sustainability. For example, “Development that meets the needs of the present without compromising the ability of future generations to meet their own needs” is the working definition provided by the report Our Common Future, published in 1987 by the World Commission on Environment and Development [12]. In most cases, the terms renewable polymers and sustainable polymers are used with overlapping mean-ings and without any distinction. Contrary to common belief, it should be noted that not all renewable polymers are sustainable. Typically, renewable polymers are made from renewable chemical feedstocks. However, to be sustainable, those renewable polymers should be more environmentally friendly to produce and use. Sustainable polymers should demand less non‐renewable chemicals or energy for their synthesis and processing, make less pollution emissions, and be amenable to be decomposed and even composted after reaching their service lifetime (Figure 1.1).

The past two decades have overseen a great level of scientific advancements that have paved paths toward the primary stages of an era of sustainability, car-bon neutrality, and independence from petroleum sources for making polymeric materials. Rapid expansion of this field can be visualized by the exponential

Biomassfeedstock

Monomers,polymers

Polymer productsPolymer products

CO2 + H2O+ compost

WasteWaste

Monomers,polymers

Petrochemicalfeedstock

Figure 1.1 A comparison between traditional petrochemical‐based polymers and sustainable polymers.

1.2 Suutainabbe obyyeru 3

increase in the number of scientific reports published on sustainable polymers in recent years (Figure 1.2), appearance of dedicated scientific journals such as ACS Sustainable Chemistry and Engineering and the steady increase of the market share of renewable bio‐based material products, for example, NatureWorks Ingeo™, DuPont™ Sorona®. Although the worldwide production capacity of bio‐based polymers is only 5.7 million tons (2% of total polymer capability) in 2014, it is expected to triple to nearly 17 million tons by 2020. The compound annual growth rate (CAGR) for the production capacity of bio‐based polymers is impres-sive at about 20%, whereas the CAGR for the petroleum‐based polymers is at 3–4% [13].

The principal aspects of the concept of sustainable materials are to utilize renewable biomass resources for raw materials as opposed to petrochemical sources and to ideally incorporate degradability to the novel materials such that sustainable polymers inherit a cyclic life cycle considering the time factor.

As illustrated in Figure 1.3, the plastic industry has a considerable influence on global carbon cycle. “Fossil‐sourced” carbon dioxide release is so overwhelm-ing that natural photosynthesis or other natural sinks cannot effectively moder-ate for the equilibration of the global ecosystem. However, a material feedstock transition from fossil‐based chemicals to the renewable biomass‐derived com-pounds for the production of sustainable polymer materials would diminish their contribution to the greenhouse effects because of their low carbon or car-bon neutral characteristics. As against the geographically uneven distributions of world‐wide fossil oil resources, natural biomass is widely available in many geographic areas for the development of local or regional supply of chemical and material feedstock resources without significant technological interven-tion. In addition, the market price fluctuations would be much favorable com-pared to those from crude oil resources and can provide a steady and stable supply over a long period of time.

1995 2000 2005 2010 20150

200

400

600

800

1000

Num

ber

of P

ublic

atio

ns

Year

Figure 1.2 Scientific publications with the keyword “sustainable polymers” published from 1995 to 2016. (SciFinder.)

1 Introduction4

1.3 Biomass Resources for Sustainable Polymers

Global primary production of the biosphere exceeds 100 billion metric tons of carbon per year, which include contributions from both terrestrial and marine communities [14]. It is obvious that this primary production either mostly ends up in food chains or decays and sediments. Useful raw materials for making sus-tainable polymers are hidden in the biomass. Unfortunately, the utilization of biomass for sustainable polymer production is lagging behind largely due to the price and property competitiveness of fossil oil counterparts, as well as their well‐established routine processing technologies for polymer industry. In addition, as the human population grows rapidly, the demand for biomass usage for food and energy purposes has perceived an escalating interest. Nevertheless, a modern “gold rush” is witnessed in recent years to unlock the true potential of biomass chemicals. Generation of sustainable polymers from agricultural feedstocks such as sugar cane, soybean, corn, potatoes, and other plants has limitations due to competing food necessities. Therefore, there are significant efforts that focus on developing nonfood renewable biomass including waste resources, such as ligno-cellulosic resources, paper mill waste, agricultural waste, and food waste.

1.3.1 Natural Biopolymers

Naturally occurring biopolymers such as rubber, cotton, and starch were used extensively for a long time before the invention of synthetic polymers less than a century ago. In recent years, the reviving efforts of biopolymer research in mate-rials science have been very active. In particular, there is enormous growth in the research on biopolymers such as cellulose, chitosan, and lignin (Figure 1.4) to discover novel hybrid materials with improved properties as well as for commercialization.

CO2 + H2O

Platform chemicalspolymersfuels

Fossilresources

Biomass

Pho

tosy

nthe

sis

Deg

rada

tion

Degradation

Incineration/combusion

Recycle

Biore�nery

Millions of years

Petroleum re�nery

Figure 1.3 A schematic diagram to illustrate the concepts of sustainable polymers from biomass.

1.3 ­ioyauu Reuourceu orrSuutainabbe obyyeru 5

Chapter 2 of this book by George Chen et al. is dedicated to the description of the research frontiers of polyhydroxyalkanoates (PHAs), a family of biodegrad-able linear polyesters, which are produced by bacterial fermentation of sugars and lipids [15]. Their structural diversity and analogy to plastics makes them viable candidates to replace synthetic thermoplastics. With modern technolo-gies, the PHA research has expanded to produce block copolymers and graft copolymers to tailor the thermal and other physical properties of PHAs using a variety of bacteria including new isolates and metabolically engineered species.

Recent advances in biotechnology have made the use of biochemical means such as microbial fermentation of various biomass feedstocks in the production of bio‐based monomers such as lactic acid, succinic acid, and itaconic acid to be more cost‐effective. These monomers are then polymerized using conventional methods. Examples of polymers include poly(lactic acid), poly(butylene succinate), poly(ethylene), and poly(itaconic acid) (Figure 1.5). Polylactide or poly(lactic acid) is a type of thermoplastic polyester that is one of the most p romising commercialized renewable polymers due to its biodegradability, bio-compatibility, and sufficient mechanical properties. Long chain branched poly-lactides (LCB PLAs) have been introduced to overcome shortages of linear versions. In Chapter 3, Zhigang Wang et al. summarize and discuss the recent

Cellulose

Chitosan

Lignin

O

OH

HOOH

OO

HOOH

O

OH n

OHO

OH

HONH2

n

O

OH

HONH2

OO

OH

HONH2

O OH

O

O

OO

O

O

O

O

O

O

O

O

OH

OH

O

O

O

O

RO

O

OH

OH

OR

OHOH

OH

OHOH

OH

OLignin

OHOH

OH

OH

HO

HOHO

HO

HOHO

HO

HO

HO

HO

HO

HO

OCH3

OCH3

OCH3

OCH3

OCH3

OCH3

OCH3

OCH3OCH3

OCH3

OCH3

OCH3

H3CO

H3CO

H3CO

H3CO

H3CO

H3CO

H3CO

H3CO

H3CO

CH3O

H3CO

Figure 1.4 Examples of a few naturally occurring biopolymers.

OO O O

O

O

Poly(butylene succinate)Poly(lactic acid)

Figure 1.5 Sustainable polymers derived from biotechnologically derived monomers.

1 Introduction6

advances in the fabrication and structural characterizations of LCB PLAs from the “bottom‐down” strategy.

1.3.2 Monomers and Polymers from Biomass

Compared to chemicals from fossil oil refinery, one major drawback in bio-mass feedstocks is its direct conversion into high value chemicals that can be used for polymerizations [16]. Technological infancy for such enterprises as well as the operating cost makes it far from feasible for large‐scale production. However, modern chemists and material scientists have cracked down most of these problems and have achieved varying degrees of success. Top biomass platform molecules produced from sugars, which were recognized by the US Department of Energy, are shown in Figure 1.6 [17]. A recognized approach for transforming raw biomass into marketplace chemicals is provided by the concept of biorefinery [18]. In a biorefinery, raw biomass feedstock is pro-cessed to generate value‐added platform chemicals. The products from biore-finery are  expected to replace fossil oil‐based products resulting from petrochemical refinery.

O

HOO

OH

Succinic acid

O

HOO

OH

Fumaric acid

OH

O

OHO

HO

Malic acid

3-Hydroxybutyrolactone

OO

HO

O

O

OH

Levulinic acid

OHOH

HO

Glycerol

OHOH

OH

OH

OHHO

Sorbitol

HOOH

OH

OHOH

1.3 ­ioyauu Reuourceu orrSuutainabbe obyyeru 7

Besides these chemicals, hydrocarbon‐rich biomass such as terpenes including pinene, limonene, resin acids (Figure 1.7), and furans, as well as fatty acids from vegetable oils, cashew nut shell liquid are promising candidates for sustainable polymer preparation [7, 8, 11, 19, 20].

Terpenes are the largest and most abundant class of natural hydrocarbons found in nature. Various olefinic terpenes have been incorporated into polymeric materials. Sustainable vinyl polymers prepared via controlled polymerization of terpenes is discussed in Chapter 4 by Masami Kamigaito et al. Resin acids are naturally produced by conifer trees and the production is more than 1 million tons annually. This largely overlooked resource is gaining interest as a source for the polymer industry. Chapter 5 by Jinwen Zhang et al. delivers a general over-view of properties and novel applications of rosin and turpentine‐based polyure-thane materials. Fuxiang Chu et  al. provide a well‐detailed discussion about rosin‐derived monomers and their progress in polymer application in Chapter 6. Chapter 7 by Phil Hurd et al. is based on the progression of crude tall oil feed-stock to fractionated products including terpenes isolated from crude sulfate turpentine, tall oil fatty acids, and rosin acids from the distillation process involved in pine chemicals industry.

Triglycerides from natural plant oils are a widely abundant source of biomass to produce sustainable polymers and materials. Various types of thermoset poly-mers have been developed using plant oils. In Chapter 8, Chuanbing Tang et al. review recent advances on mono‐functional monomers derived from plant oils that have been pursued for the preparation of re‐processable linear polymers with pendent fatty chains. Energy efficient and environmentally attractive technolo-gies such as photo‐initiated cationic polymerization are in demand for sustaina-ble polymer research. Structure–property relationships of epoxy thermoset networks developed for UV‐cure coating applications using photoinitiated cati-onic polymerization of epoxidized vegetable oils are provided in Chapter 9 by Chang Y. Ryu et al.

Lignocellulosic biomass originated during soybean harvesting and industrial soybean grain and sugarcane are useful sources of chemicals and polymers such as cellulose micro/nanofibrils and nanocrystals, polyols, and lignin. Chapter 10 by Delia R. Tapia‐Blácido et al. describes the recent advances in biopolymers from sugarcane and soybean lignocellulosic biomass. Starch‐based thermo-plastic products have been used in many areas, such as food packaging, coat-ing/adhesions/laminations. Renewable and biodegradable polymer materials

Beta-pinene

3-Carene

OHO

Abietic acid

OHO

Dehydroabietic acid

Limonene

Camphene

Figure 1.7 Terpene‐based compounds used in renewable polymers.

1 Introduction8

developed utilizing wheat gluten has provided a promising area of sustainable polymers from biomass. In Chapter 11, Xiaoqing Zhang et al. discusses in detail about the current status of investigation on wheat gluten‐based materials.

Non‐hydrocarbon molecular biomass including carbon dioxide (CO2), carbon disulfide (CS2), and carbonyl sulfide (COS) is useful in the preparation of copoly-mers with epoxides that afford C1‐based polycarbonate polymers (Figure 1.8). Such polymers could be promising to directly reduce the impact of excessive lev-els of CO2 produced by burning of fossil resources. However, the major drawback is the poor activity of the reactants to undergo polymerization. To circumvent that, copolymerization optimization and new catalysts are being investigated.

Chapter 12 by Xing‐Hong Zhang et al. introduces the recent efforts on the C1 copolymerization of CO2 and its sulfur analogs (COS and CS2), covering catalyst systems, and a variety of epoxides including several biomass‐derived molecules. In Chapter 13, Darbha Srinivas et al. put forth advancements made about double‐metal cyanide catalyst design in CO2/epoxide copolymerization.

1.4 Conclusions

This book intends to give an overview of sustainable polymers from renewable biomass with specific areas of research that are worthy of a comprehensive dis-cussion. As plastics are becoming increasingly ubiquitous materials in our mod-ern society for a wide range of applications from commodity to advanced technology, our quality and style of living depends on the increasing develop-ment and usage of polymers from renewable sources. We envision that, in the future, sustainable polymers from natural biomass will significantly replace the petroleum‐derived polymers. It is simply a matter of time for modern polymer science and technology to be relieved of its dependence on petroleum, as the fos-sil oil resources will be geographically localized and eventually depleted. Therefore, this book is written to highlight the significant achievements that have been made on our quests to transform technology from petrochemical‐based polymers to bio‐based sustainable polymers.

References

1 PlasticsEurope (2015) Plastics–the Facts 2014/2015, http://www.plasticseurope.org/Document/plastics‐the‐facts‐20142015.aspx?FolID=2 (accessed 10 September 2016).

O

+

O O

OnCatalyst

CO2

Figure 1.8 Copolymerization of limonene oxide and CO2.

9Re erenceu

2 UNEP http://www.unep.org/ietc/Portals/136/Conventional%20vs%20biodegradable%20plastics.pdf (accessed 10 September 2016).

3 Thompson, R.C., Moore, C.J., Vom Saal, F.S. and Swan, S.H., (2009) Plastics, the environment and human health: current consensus and future trends. Philos. Trans. R. Soc. Lond., B, Biol. Sci., 364, 2153–2166.

4 Mekonnen, T., Mussone, P., Khalil, H., and Bressler, D. (2013) Progress in bio‐based plastics and plasticizing modifications. J. Mater. Chem. A, 1, 13379–13398.

5 Belgacem, M.N. and Gandini, A. (2011) Monomers, Polymers and Composites from Renewable Resources, Elsevier.

6 Azapagic, A., Emsley, A., and Hamerton, I. (2003) Polymers: the Environment and Sustainable Development, John Wiley & Sons, Ltd.

7 Wilbon, P.A., Chu, F., and Tang, C. (2013) Progress in renewable polymers from natural terpenes, terpenoids, and rosin. Macromol. Rapid Commun., 34, 8–37.

8 Yao, K. and Tang, C. (2013) Controlled polymerization of next‐generation renewable monomers and beyond. Macromolecules, 46, 1689–1712.

9 Williams, C.K. and Hillmyer, M.A. (2008) Polymers from renewable resources: a perspective for a special issue of polymer reviews. Polym. Rev., 48, 1–10.

10 Gandini, A. (2011) The irruption of polymers from renewable resources on the scene of macromolecular science and technology. Green Chem., 13, 1061–1083.

11 Holmberg, A.L., Reno, K.H., Wool, R.P., and Epps, T.H. III (2014) Biobased building blocks for the rational design of renewable block polymers. Soft Matter, 10, 7405–7424.

12 The Brundtland Commission (1987) Our Common Future, The Report of the World Commission on Environment and Development (WCOED), Oxford University Press, Oxford.

13 Nova http://www.bio‐based.eu/market_study/ (accessed 10 September 2016).14 Field, C.B., Behrenfeld, M.J., Randerson, J.T., and Falkowski, P. (1998) Primary

production of the biosphere: integrating terrestrial and oceanic components. Science, 281, 237–240.

15 Reddy, C.S.K., Ghai, R., Rashmi, and Kalia, V.C. (2003) Polyhydroxyalkanoates: an overview. Bioresour. Technol., 87, 137–146.

16 Bozell, J.J. (2008) Feedstocks for the future–biorefinery production of chemicals from renewable carbon. Clean–Soil Air Water, 36, 641–647.

17 Werpy, T., Petersen, G., Aden, A., Bozell, J., Holladay, J., White, J., Manheim, A., Eliot, D., Lasure, L., and Jones, S. (2004) Top Value Added Chemicals from Biomass. Volume 1‐Results of Screening for Potential Candidates from Sugars and Synthesis Gas, DTIC Document.

18 Cherubini, F. (2010) The biorefinery concept: using biomass instead of oil for producing energy and chemicals. Energy Convers. Manage., 51, 1412–1421.

19 Quirino, R.L., Garrison, T.F., and Kessler, M.R. (2014) Matrices from vegetable oils, cashew nut shell liquid, and other relevant systems for biocomposite applications. Green Chem., 16, 1700–1715.

20 Gandini, A., Lacerda, T.M., Carvalho, A.J.F., and Trovatti, E. (2016) Progress of polymers from renewable resources: furans, vegetable oils, and polysaccharides. Chem. Rev., 116, 1637–1669.

11

Sustainable Polymers from Biomass, First Edition. Edited by Chuanbing Tang and Chang Y Ryu.© 2017 Wiley-VCH Verlag GmbH & Co. KGaA. Published 2017 by Wiley-VCH Verlag GmbH & Co. KGaA.

2

2.1 Introduction

The development of modern science, technology, and industry has brought pros­perity and convenience to human society. Some of them are attributed to the fossil raw materials that are used for the production of many useful chemicals [1, 2]. Yet, many problems arise under the petroleum‐based production mode. Excessive usage of petroleum led to energy, resource, and environmental crisis [3]. Under such conditions, there is an urgent need for sustainable development. Nowadays, industrial biotechnology has been developed for sustainable produc­tion of bio‐based chemicals and polymers. Abundant biomass can be used as carbon sources to produce bio‐based materials that are considered as renewable, environmentally friendly, and sustainable products [4].

Polyhydroxyalkanoates (PHA), a family of biodegradable and biocompatible polyesters with diverse structures, are important members of bio‐based materials [5–7]. PHA can be accumulated in many microorganisms as carbon and energy storage inclusions under various stress conditions [8]. With many environmen­tally friendly properties such as biodegradability and biocompatibility, PHA have been investigated for many years and considered to be promising biomaterials for applications including packaging plastics, medical materials, drug carriers, biofuels, and food additives [5, 9].

The multiple properties of PHA can be attributed to its diverse structures. According to the number of carbon atoms, PHA monomers can be divided into short chain length (scl) ones consisting of 3–5 carbon atoms (C3─C5) resulting in scl PHA, and medium chain length (mcl) ones with 6–14 carbon atoms (C6─C14) resulting in mcl PHA (Figure 2.1) [6, 10]. Short chain length–medium chain length (scl–mcl) PHA can be formed via the polymerization of these two types of monomers. Another classification method of PHA is based on the mono­mer arrangement. Homopolymers, random copolymers, block copolymers, and graft polymers are named on the basis of monomer arrangement and micro­structures (Figure 2.2) [11, 12].

Many microorganisms such as Ralstonia eutropha [13, 14] and Pseudomonas putida [15] were found to be natural PHA producers. Apart from these organ­isms, some bacteria were constructed to produce PHA via metabolic engineering

Polyhydroxyalkanoates: Sustainability, Production, and IndustrializationYing Wang and Guo‐Qiang Chen

2 Polyhydroxyalkanoates: Sustainability, Production, and Industrialization12

Hydroxyalkanoate

Homopolymers

Random copolymers

Block copolymers

Graft polymers

Small moleculesor large polymers

Figure 2.2 PHA classifications based on the microstructure [11, 12].

and synthetic biology [7, 16]. Along with the development of new methods, many engineered bacteria have been constructed and employed in the industrial pro­duction of various PHA (Table 2.1) [5]. Furthermore, novel PHA with designed structures can be synthesized via manipulation of metabolic pathways or synthetic parts.

PHA granules

Short chain length PHA monomers Medium chain length PHA monomers

3HDD3HD3HO3HHx3HV3HB

O

O

O O

O O

O

O

O O

O O

Figure 2.1 Intracellular PHA and the classification of its monomers. The white granules are PHA accumulated in bacteria. 3HB, 3‐hydroxybutyrate; 3HV, 3‐hydroxyvalcrate; 3HHx, 3‐hydroxyhexanoate; 3HO, 3‐hydroxyoctanoate; 3HD, 3‐hydroxydecanoate; 3HDD, 3‐hydroxydodecanoate.

2.1 Introduction 13

Although the industrial production of PHA has been explored for many years, there is still a long way to go to allow for large‐scale production for sizable mar­kets. Similar to most of the microbially based biological production processes, one of the main reasons that PHA cannot compete with traditional petroleum‐based chemical products is its high production cost [21, 22]. Since petroleum price does not raise and in fact is decreasing recently, most of the markets are occupied by these petroleum‐based products. Taking the bioplastic packaging market as an example, PHA have only a limited market share of 1.4% [23]. Therefore, it is necessary to reduce the cost of PHA production in order to increase its competitiveness. PHA production cost includes cost of substrates, energy, water, and equipment and process complexity (Figure 2.3) [24, 25]. For a long time, many efforts have been made to develop low‐cost PHA production processes [7, 26, 27]. Three general points have to be considered. Since substrates shared the biggest proportion of cost, substrates should be cheap and abundant so that the cost can be lowered from the beginning of the PHA production pro­cess [26]. Secondly, energy saving and continuous processing are also key to reducing cost [28]. Thirdly, the problem of consuming too much precious fresh water needs to be avoided [29, 30]. Meanwhile, the improvement of PHA pro­duction abilities is complementary to reducing the cost. More research is also needed to develop technology for increasing PHA contents in the host strains. In addition to reducing the production cost, another consideration to make PHA

Table 2.1 Thermal and mechanical properties of typical PHAs and traditional plastics [17–20].

PHA samples Tma) (°C) Tg

b) (°C) σmtc) (Mpa) εb

d) (%)

P3HB 177 4 43 5P4HB 60 −51 50 1000P(3HB‐co‐11 mol% 4HB) 131.5 −4.4 20.3 698P(3HB‐co‐18 mol% 4HB) 127.9 −9.2 9.9 729P(3HB‐co‐20 mol% 3HV) 145 −1 32 ‐P(3HB‐co‐10 mol%3HHx) 151 0 21 400P(3HB‐co‐17 mol%3HHx) 120 −2 20 850P(3HB‐co‐25 mol%3HHx) 52 −4 −‐ −‐HDPE 135 ‐ 29 ‐PP 186 −10 38 400

P3HB: poly(3‐hydroxybutyrate); P4HB: poly(4‐hydroxybutyrate); P(3HB‐co‐11 mol% 4HB), P(3HB‐co‐18 mol% 4HB): poly(3‐hydroxybutyrate‐co‐4‐hydroxybutyrate) with different 4HB contents; P(3HB‐co‐20 mol% 3HV): poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalcrate) with 20 mol% 3HV; P(3HB‐co‐10 mol%3HHx), P(3HB‐co‐10 mol%3HHx), P(3HB‐co‐10 mol%3HHx): poly(3‐hydroxybutyrate‐co‐3‐hydroxyhexanoate) with different 3HHx contents; HDPE: high density polyethylene; PP: polypropylene.a) Tm, melting temperature.b) Tg, glass transition temperature.c) σmt, maximum tension strength.d) εb, elongation at break.

2 Polyhydroxyalkanoates: Sustainability, Production, and Industrialization14

more competitive is to expand their diversity so that more high value‐added products can be developed and applied in a wider area.

2.2 PHA Diversity and Properties

2.2.1 PHA Diversity

The study of PHA has been ongoing for more than 70 years. Various PHA were synthesized over the past years. Monomer variations and polymer chain struc­tures contribute to the diversity of PHA.

Dating back to 1926, the first PHA named poly(3‐hydroxybutyrate) or P3HB was found [17, 31]. P3HB was the earliest studied PHA. Subsequently, more PHA including both scl‐ and mcl‐ ones were synthesized and investigated [10, 32]. Besides P3HB, typical scl PHA include poly(3‐hydroxypropionate) or P3HP [33], poly(4‐hydroxybutyrate) or P4HB [34], poly(3‐hydroxyvalerate) or PHV [35] as  well as their copolymers such as poly(3‐hydroxybutyrate‐co‐3‐hydroxy propionate) (P3HB3HP) [36], poly(3‐hydroxypropionate‐co‐4‐hydroxy­butyrate) (P3HP4HB) [37], poly(3‐hydroxybutyrate‐co‐4‐hydroxybutyrate) (P3HB4HB) [38], and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV) [11, 39]. Mcl PHA were also studied in the past few decades. Homopolymers of mcl PHA include poly(3‐hydroxyhexanoate) or PHHx [40], poly(3‐hydroxy­heptanoate) or PHHp [15], poly(3‐hydroxyoctanoate) or PHO [15], poly(3‐hydroxydecanoate) or PHD [41], poly(3‐hydroxydodecanoate) or PHDD, and poly(3‐hydroxynonanoate) or PHN [42]. In comparison, copolymers of mcl PHA such as poly(3‐hydroxyoctanoate‐co‐3‐hydroxydecanoate) or P(3HO‐co‐3HD) were more frequently and conveniently synthesized [43].

After many years of research, it has become possible to synthesize PHA with designed structures via metabolic engineering or synthetic biology approaches. This dramatically expands the diversity of PHA. Some new PHA with novel microstructures have been synthesized in recent years. Two or more different polymer chains covalently bonded result in block copolymers. Syntheses of PHA block copolymers have been achieved previously [44]. The successful synthesis

Consituents of the production cost

Substrates

Energy

WaterEquipments

Others

Figure 2.3 Constituents of PHA production cost.