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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
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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
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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
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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
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of P
ublic
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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.