The Chemistry of Bio-based Polymers
Description
The factors influencing the degradation and biodegradation of polymers used in food packaging, exposed to various environments, are detailed at length. The book covers the medical applications of bio-based polymers, concentrating on controlled drug delivery, temporary prostheses, and scaffolds for tissue engineering. Professor Fink also addresses renewable resources for fabricating biofuels and argues for localized biorefineries, as biomass feedstocks are more efficiently handled locally.
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Johannes Karl Fink is Professor of Macromolecular Chemistry at Montanuniversität Leoben, Austria. His industry and academic career spans more than 30 years in the fields of polymers, and his research interests include characterization, flame retardancy, thermodynamics and the degradation of polymers, pyrolysis, and adhesives. Professor Fink has published several books on physical chemistry and polymer science including A Concise Introduction to Additives for Thermoplastic Polymers (Wiley-Scrivener 2009), The Chemistry of Biobased Polymers (Wiley-Scrivener 2014), Polymer Waste Management (Wiley-Scrivener 2018) and 3D Industrial Printing with Polymers (Wiley-Scrivener 2019).
Content
Preface i
1 An Overview of Methods and Standards 1
1.1 History of Biodegradable Plastics 1
1.2 Green Chemistry 3
1.2.1 Genetic Engineering 5
1.3 Commercial Situation 8
1.4 Environmental Situation 9
1.4.1 Problems with Bio-based Composites 13
1.4.2 Biodegradation 14
1.5 Properties of Biodegradable Polymers 19
1.6 Special Methods of Synthesis 19
1.6.1 Conventional Methods 19
1.6.2 Click Chemistry 20
1.6.3 Enzymatic Polymerization 21
1.6.4 Chemoenzymatic Polymerization 24
1.6.5 Vine-Twining Polymerization 26
1.6.6 Bacterial Synthesis 28
1.7 Biodegradability Standards 28
1.7.1 Guidelines for the Development of Standards 29
1.7.2 Specifications for Compostable Plastics 32
1.7.3 Ultimate Anaerobic Biodegradability 33
1.7.4 Aerobic Biodegradability 33
1.7.5 Biodegradability of Plastics in Seawater 36
1.8 Test of the Biological Origin 38
References 45
Part I Bio-based Polymers Degradation and Chemistry 57
2 Vinyl-Based Polymers 59
2.1 Polyolefins 59
2.1.1 Degradability 60
2.1.2 Degradation Mechanism 60
2.1.3 Prodegradants 61
2.2 Poly(styrene)Elastomers 63
2.3 Poly(vinyl alcohol) 63
2.3.1 Plasticized Compositions 63
2.3.2 Hydrogels 67
2.3.3 Antibacterial Film 68
2.4 Poly(vinyl butyral) 70
2.4.1 Blends with Poly(3-hydroxybutyrate) 71
2.4.2 Blends with Poly(lactic acid) 72
2.4.3 Paper Coatings 73
2.4.4 Fibers 74
2.4.5 Membranes 75
2.4.6 Solar Cells 77
2.4.7 Adhesive for Safety Glass 79
References 82
3 Acid and Lactone Polymers 87
3.1 Poly(lactic acid) 87
3.1.1 Production Processes 87
3.1.2 Fibers 96
3.1.3 Influence of Fabrication Methods and Kenaf Fiber Length 98
3.1.4 Kenaf Fibers for Reinforcement of PP 99
3.1.5 Films 99
3.1.6 Fertilizer Solutions 101
3.1.7 Reinforced Composites 102
3.1.8 Nanocomposites 103
3.1.9 Membranes 105
3.1.10 Antibacterial Composites 106
3.1.11 Laminated Composites from Kenaf Fiber 107
3.1.12 Copolyesters 108
3.1.13 Transparent Crystalline Poly(lactic acid) 109
3.1.14 Laminated Biocomposites 110
3.2 Poly(glycolic acid)s 111
3.2.1 Glycolic Acid 111
3.2.2 Polymers, Copolymers, and Blends 112
3.2.3 Condensation Polymer of Glycerol 112
3.3 Butyrolactone-Based Vinyl Monomers 114
3.3.1 Tulipalin A 114
3.3.2 a-Methylene-¿-valerolactone 116
3.4 Poly(caprolactone) 119
References 122
4 Ester and Amide Polymers 129
4.1 Poly(ester)s 129
4.1.1 Poly(hydroxyalkonate)s 129
4.1.2 Methyl-10-undecenoate 130
4.1.3 Poly(butylene adipate) Copolyesters 135
4.1.4 Poly(hydroxyalkanoate)s 135
4.1.5 Poly(hydroxybutyrate) 137
4.1.6 Poly(hydroxyvalerate) 139
4.1.7 Poly(3-hydroxyhexanoic acid) 142
4.1.8 Poly(ß-hydroxyoctanoate) 145
4.1.9 Poly(¿-glutamicacid) 148
4.1.10 Poly(butylene succinate) 150
4.1.11 Dianhydrohexitol-Based Polymers 153
4.1.12 Aliphatic-Aromatic Copolyesters 158
4.1.13 Succinate-Based Polyesters 165
4.1.14 Sebacate-Based Polyesters 165
4.1.15 2,5-Furandicarboxylic Acid-Based Polyesters 169
4.1.16 Unsaturated Polyesters 170
4.1.17 Sulfonated Polyesters 174
4.2 Plant Oil-Based Biopolymers 177
4.2.1 Water Treatment 179
4.2.2 Plant Oils with Acrylic Moities 181
4.2.3 Plant Oils with Phosphorus Moities 182
4.2.4 Vanillin-Based Monomers and Polymers 185
4.2.5 Soybean Oil Epoxidized Acrylate 189
4.2.6 Vegetable Oil Thermosets 190
4.3 Poly(amide)s 192
4.3.1 Soy-Based Bioplastic and Chopped Industrial Hemp 192
4.3.2 Soybean-Based Composites 193
References 203
5 Carbohydrate-Related Polymers 213
5.1 Starch 213
5.1.1 Starch Modification 214
5.1.2 Reactive Dye Removal 218
5.1.3 Starch Granules 219
5.1.4 Baked Foams 224
5.1.5 Starch Composite Foam 226
5.1.6 High Starch Polymer 231
5.1.7 Destructurization of Natural Starch 232
5.1.8 Melt Processable Starch 233
5.1.9 Starch-Based Aerogels 235
5.1.10 Spinning Processes for Starch 236
5.1.11 Pre-gelled Starch Suspensions 239
5.1.12 Processing of Natural Starch 240
5.1.13 Granular Starch as Additive to Conventional Polymers 241
5.2 Cellulose 243
5.2.1 Liquid Crystalline Derivatives 244
5.2.2 Cellulose Fibers 246
5.2.3 Cellulose Nanopapers 253
5.2.4 Modified Cellulose Fibers 256
5.3 Cellulose Ethers 259
5.4 Nonionic Cellulose Ethers 262
5.5 Cellulose Esters 263
5.6 Cellulose Ether Esters 265
5.7 Lignin 267
5.7.1 Lignocellulose Biorefinery 269
5.7.2 Acid Hydrolysis 271
5.7.3 Alkaline Hydrolysis 272
5.7.4 Enzymatic Hydrolysis 273
5.7.5 Reductive or Oxidative Fractionation 273
5.7.6 Combined Pretreatment Methods 274
5.7.7 Pyrolysis 275
5.7.8 Acidic Conversion 277
5.7.9 Reductive Conversion 277
5.7.10 Oxidative Conversion 277
5.8 Biodegradable Nanocomposites 278
5.8.1 Oxidation of Spruce and Pulps 279
5.8.2 Modified Cellulose Nanofibers 280
5.8.3 Bio-based Epoxy Nanocomposites 281
5.9 Chitin 281
References 286
6 Other Polymer Types 297
6.1 Terpenes 297
6.1.1 Grafted Terpene 297
6.1.2 Thiol-ene Additions 298
6.1.3 Pinenes 299
6.2 Poly(urethane)s 304
6.2.1 Poly(ester urethane)s 305
6.3 Cationic Lipopolymers 306
6.4 Plastics from Bacteria 307
6.4.1 Poly(ß-hydroxyalkanoate)s 307
6.5 Bio-based Epoxy Resins 310
6.5.1 Poloxamers 311
6.6 Phosphate-Containing Polymers 312
6.7 Polyketals 320
6.8 Biorubber 322
6.9 Collagen 323
6.10 Pyridinium Modified Polymers 324
6.11 Commercial Biodegradable Polymers 325
References 327
Part II Applications 331
7 Packaging, Food Applications and Foams 333
7.1 Packaging 333
7.1.1 Packaging Materials 333
7.1.2 Lightweight Compostable Packaging 334
7.1.3 Laminate Coatings 335
7.1.4 PLA Resins 336
7.1.5 Protein-Derived Bionanocomposites 337
7.1.6 Lignocellulose 338
7.1.7 Tannic Acid 338
7.1.8 Starch Compositions 340
7.1.9 Heat-Sealable Paperboard 349
7.1.10 Packages with Corrosion Inhibitor 350
7.1.11 Multiwall Package 351
7.1.12 Cushioning Nuggets 352
7.1.13 Fluid Containers 353
7.2 Fibers and Nets 356
7.2.1 Multicomponent Fiber 356
7.2.2 Biodegradable Netting 357
7.2.3 Electrospun Nanofibrous Mat 358
7.3 Foams 359
7.3.1 Foamed Articles 360
7.3.2 Blends 361
7.3.3 Starch-Polyester Graft Copolymer 361
7.3.4 Foamed Gelling Hydrocolloids 361
7.4 Biodegradable Adhesive Compositions 366
7.5 Food Applications 367
7.5.1 Edible Packaging 367
7.5.2 Canola Protein-Based Biodegradable Packaging 368
7.6 Other Applications 369
7.6.1 Chewing Gum 369
7.6.2 Astaxanthin 369
7.6.3 Edible Films and Coatings 371
References 375
8 Medical Applications 383
8.1 Drug Delivery 383
8.1.1 Acacia 388
8.1.2 PLA and PLGA Copolymers 392
8.1.3 Poly(¿ -glutamic acid) 393
8.1.4 Carrageenan 394
8.1.5 Cellulose 395
8.1.6 Chitosan 396
8.1.7 Gellan Gum 396
8.1.8 Guar Gum 398
8.1.9 Hyaluronic Acid Derivatives 398
8.1.10 Khaya Gum 401
8.1.11 Locust Bean Gum 401
8.1.12 Pectin 402
8.1.13 Xanthan Gum 403
8.1.14 Tragacanth Gum 403
8.1.15 Electrospinning 405
8.1.16 Mucoadhesive Drug Delivery 412
8.2 Tissue Engineering 414
8.2.1 Scaffolds for Tissue Engineering 414
8.2.2 3D Bioprinting 417
8.2.3 Periodontal Tissue Engineering 418
8.2.4 Cell Carriers 419
8.3 Tissue Markers 419
8.4 Hydrogels 422
8.5 Microporous Materials 423
8.6 Implants 426
8.6.1 Inflammatory Problems with Implants 427
8.6.2 Eye Implants 430
8.6.3 Thermosetting Implants 434
8.6.4 Neurotoxin Implants 438
8.6.5 Water-Soluble Glass Fibers 438
8.6.6 Bone Repair 439
8.7 Shape Memory Polymers 442
8.7.1 Shape Memory Polyesters 444
8.8 Stents 444
8.8.1 Surface Erosion 447
8.8.2 Tubular Main Body 448
8.8.3 Multilayer Stents 449
8.9 Thermogelling Materials 450
8.10 Cancer Therapy 451
8.10.1 Anticancer Peptide 451
8.10.2 Synergistic Cancer Therapy 452
8.11 Wound Dressings 452
8.12 Bioceramics 453
8.13 Conjugates 454
References 456
9 Personal Care and Sanitary Goods 465
9.1 Breathable Biodegradable Composition 465
9.2 Personal Hygiene Applications 465
9.3 Sanitary Goods 466
9.4 Superabsorbent Materials 469
References 473
10 Miscellaneous Applications 475
10.1 Flooring Materials 475
10.2 Abrasives and Polishing Compositions 479
10.2.1 Cleansers 479
10.2.2 Polishing Pads 482
10.3 Lubricants 484
10.4 Renewable Cards 485
10.5 Biodegradable Irrigation Pipe 487
10.6 Thermosensitive Material 488
10.7 Biodegradable Scale Inhibitors 491
10.7.1 Phosphorus-Containing Polymer 491
10.8 Nanocomposites 492
10.9 Molded Articles from Fruit Residues 493
10.10 Fluorescent Biodegradable Particles 493
10.11 Test Cylinder Mold for Testing Concrete 496
10.12 Flexographic Inks 496
10.13 Audio Systems 498
10.14 Automotive Uses 499
10.15 Oil Well Environment 500
10.16 Green Hot Melt Adhesives 501
10.17 Mechanistic Studies 501
10.17.1OlefinIsomerization 501
References 504
11 Biofuels 507
11.1 Xenobiotics 507
11.2 Biopolymers 508
11.2.1 Poly(l-lactide) 508
11.3 Bioethanol 510
11.3.1 Pretreatment Methods 512
11.3.2 Cellulases and Hemicellulases 514
11.3.3 Production from Starch 516
11.3.4 Production from Lignocellulose 517
11.3.5 Production from Lichenan 518
11.3.6 Production from Other Sources 520
11.4 Biobutanol 523
11.5 Biodiesel 530
11.5.1 Transesterification Methods 531
11.5.2 Production from Microalgae Beats 533
11.5.3 Two-Step Catalytic Conversion 533
11.5.4 Improvement of Diesel Fuel Properties by Terpenes 534
References 537
Index 543
Tradenames 543
Acronyms 550
Chemicals 553
General Index 564
Chapter 1
An Overview of Methods and Standards
Biocomposites are considered the next-generation materials as they can be made using natural/green ingredients to offer sustainability, eco-efficiency, and green chemistry (1-3). Nowadays, biocomposites are being utilized by numerous sectors, which include automobile, biomedical, energy, toys, sports, and others.
An effort has been made to provide a comprehensive assessment of the available green composites and their commonly used in order to make materials capable of meeting present and future demands. Various types of natural fibers have been investigated with polymer matrixes for the production of composite materials that are on par with the synthetic fiber composite. Also, the requirements for green composites in various applications from the viewpoint of variability of fibers available and their processing techniques have been detailed (4).
1.1 History of Biodegradable Plastics
In the late 1980s, biodegradable plastics came into use. However, these came to be misapplied in a number of situations. The misapplication of inappropriate or incompletely developed technology led to products which often did not meet performance claims and expectations. The so-called first generation technologies often lacked one or more of the following issues (5):
- Rate or extent of biodegradation, primarily due to limitations of starch incorporation,
- Necessary physical properties and related characteristics
- An economical means to effectively and efficiently manufacture starch-based blends,
- Intermediate product compatibility with conventional plastics product conversion processes, and
- Lower limits on film thickness caused by the use of non-gelatinized starch materials.
The synthesis, processing, and technology of renewable polymers has been reviewed (6-27). Furthermore, the state-of-the-art for food packaging applications has been reviewed (28-32). Using biomass for the production of new polymers can have both economic and environmental benefits (33).
Biomass-derived monomers can be classified into four major categories according to their natural resource origins (34):
- Oxygen-rich monomers including carboxylic acids, e.g., lactic acid succinic acid, itaconic acid, and levulinic acid, but also ethers, such as furan,
- Hydrocarbon-rich monomers including vegetable oils, fatty acids, terpenes, terpenoids and resin acids,
- Hydrocarbon monomers, i.e., bio-olefins, and
- Non-hydrocarbon monomers such as carbon dioxide.
Carbon dioxide is an interesting synthetic feedstock, which can be copolymerized with heterocycles such as epoxides, aziridines, and episulfides. In 1969, Inoue reported the zinc catalyzed sequential copolymerization of carbon dioxide and epoxides as a new route to poly(carbonate)s (9, 35). The reaction is shown in Figure 1.1.
Figure 1.1 Reaction of carbon dioxide with epoxides (35).
Plants produce a wide range of biopolymers for purposes such as maintenance of structural integrity, carbon storage, and defense against pathogens as well as desiccation. Several of these natural polymers can be used by humans as food and materials, and increasingly as an energy carrier. Plant biopolymers can also be used as materials in certain bulk applications such as plastics and elastomers (36).
Lignin, suberin, vegetable oils, tannins, natural monomers like terpenes, and monomers derived from sugars are typically natural precursors for bio-based industrial polymers. Glycerol and ethanol also play a potential role as future precursors to monomers (37).
1.2 Green Chemistry
The principles and concepts of green chemistry are the subjects of several monographs (38-47). Recent progress in enzyme-driven green syntheses of industrially important molecules has been summarized (48). Studies in biotechnological production of pharmaceuticals, flavors, fragrance and cosmetics, fine chemicals, as well as polymeric materials (49) have been documented. Biocatalysis is a transformational technology uniquely suited to delivering green chemistry solutions for safer, efficient, and more cost-effective chemical synthesis.
The different catalytic processes for the conversion of terpenes, triglycerides and carbohydrates to valuable chemicals and polymers have been reviewed (50).
A basic task of green chemistry is to design chemical products and processes that use and produce less hazardous materials. The term hazardous covers several aspects, including toxicity, flammability, explosion potential and environmental persistence (51).
The synthesis of maleic anhydride illuminates a possibility of multiple pathways. Maleic anhydride can be synthesized both from benzene and from butene by oxidation. In the first route, a lot of carbon dioxide is formed as an undesirable byproduct. Thus, the first route is addressed as atom uneconomic. In Table 1.1, some uneconomic and economic reaction types in organic chemistry are opposed.
Table 1.1 Atom uneconomic and economic reaction types.
Economic Uneconomic Rearrangement reaction Substitution reaction Addition reaction Elimination reaction Diels-Alder reaction Wittig reaction Claisen reaction Grignard reactionThere were in total 12 basic principles in green chemistry (52-55). These principles are summarized in Table 1.2.
Table 1.2 Basic principles of green chemistry (53).
PrincipleEnsure that all material and energy inputs and outputs are as inherently nonhazardous as possible.
Better prevent waste than cleanup.
Minimize energy consumption and materials.
Maximize efficiency of mass, energy, space, and time.
Products, processes, and systems should be output pulled rather than input pushed.
Embedded entropy and complexity must be viewed as an investment when making design choices on recycle, reuse, or beneficial disposition.
The design goal should be targeted durability.
Unnecessary capacity or capability is not desirable.
Material diversity in multicomponent products should be minimized.
Development of products, processes, and systems must consider energy and materials flows.
The design should consider a commercial afterlife.
Material and energy inputs should be renewable.
Recently, the above-mentioned concept was extended (56). The special volume on green and sustainable chemistry and engineering has fourteen papers that were considered relevant to the present day issues and discussion, such as adequate use of raw materials and efficient energy, besides considering renewable sources for materials and energy; and changing economical canons towards circular economy. Businesses, governments and societies are facing a number of challenges along the pathway to sustainability for the well-being of future generations. Chemicals are ubiquitous in everyday activities. Their widespread presence provides benefits to societies' well-being, but can have some deleterious effects. To counteract such effects, green engineering and sustainable assessment in industrial processes have been gathering momentum in the last thirty years. Green chemistry, green engineering, eco-efficiency, and sustainability are becoming a necessity for assessing and managing products and processes in the chemical industry. Fourteen articles have been discussed, related to sustainable resource and energy use (five articles), circular economy (one article), cleaner production and sustainable process assessment (five articles), and innovation in chemical products (three articles) (56).
Catalytic processes from the viewpoint of green chemistry include catalytic reductions and oxidations methods, solid-acid and solid-base catalysis, as well as carbon-carbon bond formation reactions (57).
Novel concepts and techniques such as bio-inspired polymer design, synthetically-inspired material development are now considered to contribute to the development of natural monomers and polymers as a sustainable resource. These concepts and techniques that integrate materials synthesis, process and manufacturing options with eco-efficiency have been documented (58-62).
1.2.1 Genetic Engineering
The direct production of novel compounds in biomass crops in order to produce bioenergy as a coproduct seems to be a promising way to improve the economics of transgenic plants as biofactories (63).
Genetic engineering of plants may be used for the production of novel polymers and basic chemicals. These methods may help to alleviate the demands for limited resources and provide a platform to produce some desired compounds in bulk quantities.
Recent advances in enhancing the production of novel compounds in transgenic plants consist of a multigene transformation and the direction of the biosynthetic pathways to specific intracellular compartments.
Basically it appears feasible to produce interesting proteins, such as spider silk or collagen, novel carbohydrates, and biopolymers using transgenic plants. These compounds could replace petroleum-based plastics (63). However, there are pro and con arguments. For example, if transgenic...
