Biopolymers: Reuse, Recycling, and Disposal

Biopolymers: Reuse, Recycling, and Disposal

Michael Niaounakis

PDL HANDBOOK SERIES

Table of Contents

Cover image

Title page

Series Page

Copyright

Quotes

Foreword

Abbreviations of Biopolymers

1. Introduction to Biopolymers

1.1 Rationale for Use of Biopolymers

1.2 Types of Biopolymers

1.3 Polyesters

1.4 Poly(ether-ester)s

1.5 Aliphatic Polycarbonates

1.6 Polyamides

1.7 Poly(ester amide)s

1.8 Poly(ether amide)s

1.9 Polyurethanes (Bio-Based PUs)

1.10 Polysaccharides

1.11 Vinyl Polymers

1.12 Diene Polymers

1.13 Other Biodegradable Polymers

1.14 Biopolymer Compositions

1.15 Biodegradable Biopolymer Additives

1.16 Sources of Biopolymers

1.17 Applications and Parts

1.18 Sources of Scrap and Waste Biopolymers

References

2. Definitions and Assessment of (Bio)degradation

2.1 Define the Terms

2.2 Classification of Biopolymers

2.3 Biopolymers versus Oxodegradable Polymers

2.4 Types and Mechanisms of (Bio)degradation

2.5 (Bio)degradation Testing

References

3. Reuse

3.1 Recuperation

3.2 Restabilization

3.3 Blending Recycled Biopolymers with other Polymers

3.4 Modification of the Chemical Structure

3.5 Multiple Processing

References

4. Disposal

4.1 General

4.2 Landfilling

4.3 Biological Processes

4.4 (Bio)degradation in Water

4.5 Other Waste Disposal Systems

4.6 Destructive Thermal Processes

References

5. Physical Recycling

5.1 General

5.2 Grinding

5.3 Sorting

5.4 Drying

References

6. Chemical Recycling

6.1 Dry-Heat Depolymerization (in the Melt)

6.2 Hydrolysis/Solvolysis (Alcoholysis)

6.3 Hydrothermal Depolymerization

6.4 Enzymatic Depolymerization

6.5 Miscellaneous Processes

References

7. Degradability on Demand

7.1 Control of Degradation Rate

7.2 Suppression of (Bio)-degradability

7.3 Promotion of (Bio)-degradability

References

8. Developments and Trends in Patenting

8.1 Biopolymers and Patents

8.2 Patent Analysis

8.3 Prospects and Limitations of the Waste Treatment Options of Biopolymers

8.4 Conclusions

8.5 Development of New Waste Treatment Processes/Materials

References

9. Regulatory Aspects Framework

9.1 Standards

9.2 Certification

References

10. Economic Evaluation and Environmental Impacts

10.1 Economic Evaluation

10.2 Life Cycle Assessment (LCA)

10.3 Environmental Impacts

10.4 Health and Safety Impacts

References

Appendix I

Appendix II

Appendix III

Appendix IV. Databases Consulted

Appendix V. Further Information Sources

Institutions/Organizations

Information/Magazines/Blogs

Glossary

Patents

Applicants

Inventors

Author Index

Index

Series Page

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Copyright

William Andrew is an imprint of Elsevier

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First edition 2013

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Statement

The views and opinions expressed in this book are those of the author and do not represent the views of the European Patent Office (EPO).

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Quotes

More will I tell thee too: there is no birthOf all things mortal, nor end in ruinous death;But mingling only and interchange of mixedThere is, and birth is but its name with men.

Empedocles

From William Ellery Leonard’s The Fragments of Empedocles (Chicago: The Open Court Publishing Company, 1908).

Foreword

An outline of certain chapters of this book was presented at the Annual Symposium of Biopolymers, held in Denver, 8-10 October 2010, under the title: Disposal, Recycling and Reuse of Biopolymers - The patent perspective.

The expression biopolymer or bioplastic is used to describe two different terms at the same time, which often leads to confusion. It can mean that the polymer or plastic is biodegradable or that the raw material used is renewable or bio-based. According to the first definition a biodegradable polymer derived from fossil fuel resources is considered as biopolymer. The same applies for a non degradable bio-based polymer; for more details see Chapter 2.

The scope of this book is to present and investigate a novel phenomenon related to the recycling and/or disposal of biopolymers. At first, the idea of recycling these polymers is contradicting with the nature and scope of biodegradable biopolymers. As the current interest of biopolymers is largely based on their biodegradability, to consider recycling these polymers is to ignore one of its most important properties. However, there are good reasons for the recycling of biopolymers. Most commercial biopolymers, such as polylactide (PLA), are not degraded under ordinary conditions even in presence of microorganisms. Furthermore, the disposal of biopolymer articles has the disadvantage of discarding valuable raw materials, which could be efficiently reutilized.

Currently, biopolymers lack economies of scale, representing still a small niche within the overall plastics industry, making up less than 1% of the global plastic market, while their waste streams are small and scattered. Surprisingly enough, there is much activity in patenting on the waste treatment of biopolymers, especially from Japanese universities, institutions and companies. All these patent applicants are poised to benefit from the continuous growth of biopolymers when these materials mature and reach a critical mass, which is necessary for recycling to become profitable.

Not much attention has been paid to the waste management of these materials so far. Meanwhile, biodegradable biopolymers such as polylactide (PLA) are a serious problem when and where they enter either conventional plastics recycling (e.g. of PET) or green-waste composting streams. This problem is expected to grow as biodegradable biopolymers proliferate in residential areas. With the current rate of growth, it is expected that waste issues concerning biopolymers will emerge in the future similarly to the situation of conventional polymers that are currently used.

The book consists of 10 chapters.

Chapter 1 starts with a presentation of the main motivations for using biopolymers. A large section gives an extensive introduction to most of the existing and newly developed biopolymers and provides updated lists of their commercial products and current applications. The following section investigates the possible sources of biopolymers, including first, second and third generation feedstocks. A separate section is dedicated to the sources of scrap and waste biopolymers, which are intended for recycling.

Chapter 2 clarifies and explains the various terms used to describe biopolymers. A separate section presents the positions of the advocates of bioplastics and oxodegradable polymers and the arguments of each group against the other. In the following section are described the main types and mechanisms of (bio)degradation. The last section reviews the tests methods which have been developed for biodegradable including field tests, simulation tests and laboratory tests.

Chapter 3 describes all the possible ways of reusing discarded biopolymers. A distinction is made between reuse and physical recycling (see Chapter 5).

Chapter 4 examines all the known techniques for the disposal of biopolymers, including landfilling, disposal in soil or water and composting (industrial or home). A separated section summarizes the various microbes (aerobic and anaerobic) and enzymes used for the biodegradation of biopolymers. The following section examines alternative waste disposal systems. The last section describes the destructive thermal methods such as incineration (combustion) and pyrolysis.

Chapter 5 examines the various methods for the physical or mechanical recycling of biopolymers including techniques for identifying and sorting materials by polymer type. A separate section reviews the various marker systems including the Resin Identification Codes (RIC) and fluorescent additives.

Chapter 6 examines the various methods for the chemical recycling of biopolymers including hydrolysis/alcoholysis, dry heat depolymerization, hydrothermal depolymerization, and the relatively new enzymatic depolymerization technique.

Chapter 7 examines the various techniques of modifying and/or controlling the degradation rate of biopolymers, by suppressing or accelerating the degradation speed at will.

Chapter 8 analyzes and correlates trends in patenting related to the waste management of biopolymers. The methodology includes the collection of statistical data all over the world for the period from 01.01.1990 to 31.08.2012. A separate section presents the prospects and limitations of the main waste treatment options for biopolymers. The next section summarizes the current state of patents in the prior art. The last section reviews the developments of new waste treatment processes and biopolymers.

Chapter 9 presents the regulatory framework of biopolymers by grouping all the international standards related to recycling, disposal, biodegradation (aerobic and anaerobic), composting, and eco-toxicity. A separate group of standards refers to the determination of bio-based content. Other groups of standards refer to Life-Cycle-Assessment (LCA) and eco-labeling. A separate section describes the process of certification.

Chapter 10 constitutes of three parts. The first part reviews the few available economic analyses on the disposal and recycling of waste biopolymers. The second part presents life cycle assessment (LCA) analyses of the main biopolymers, i.e., starch, PLA and polyhydroxyalkanoates (PHAs). The third part examines the possible environmental and health effects resulting from the production, use and waste treatment of biopolymers.

The Appendix contains three tables: Table 1 is a collection of the bibliographic data of all patents related to recycling, reuse or disposal of biopolymers. Table 2 is a collection of the bibliographic data of the patents related to biodegradation on demand. Table 3 is a collection of the bibliographic data of the supplementary patents, which do not refer necessarily to biopolymers, and are used as references to processes and/or materials mentioned in the text.

This book is unique in its coverage encompassing scientific publications as well as patents. Emphasis has been given to patents, since patents refer predominantly to industrial applications and have a potential economic value. Patents, although they represent a substantial part of literature, till recently they were underrepresented in the cited bibliography. Patents are innovative, have an industrial applicability and they are not self-repeated. Although they are not peer reviewed, they have been searched and examined. Most of them come from major industries and international laboratories and the reason for this is possibly the high costs in obtaining and maintaining a patent.

It has to be clarified that the book is not a mere list of patents, but rather a critical review of all the available technologies on the issue of the waste management of biopolymers. A patent application is drafted on the so-called problem-solution approach; this means that a would-be inventor drafts its patent application by outlining the shortcomings of the prior art and proposing solutions to the stated problem. By summarizing and analyzing all the critical comments of several inventors/applicants on every prior art of each technology, the author was able to build up a clear opinion on the benefits and weaknesses of each technology. Although all this information is indeed available online, it is the author’s opinion that is almost impossible for a would-be researcher to retrieve all the available patent literature by simple searching techniques, without prior expertise. At least for the issue of disposal and recycling of biopolymers most of the available patent literature is in Japanese with only a short abstract in English. On the basis of the abstract, an English speaker may consult online a machine translation of the text, which is a very tedious and not always reliable procedure. Furthermore, the relevant literature is scattered in many technical fields making the retrieval and/or combination of all available information difficult.

The book tries to be neutral on several issues surrounding the use of biopolymers and their recycling, reuse or disposal and to present all different arguments (pros and cons). In this context ground is given to both fighting camps in the field of degradable polymers, bioplastics and oxodegradable polymers, to present their position. Furthermore, the book keeps a critical eye on unjustified claims of properties which cannot and have not yet been validated or the false use of the term bioplastic or biopolymer for marketing purposes. In the same context, it is noted that there are not enough full scale assessments (LCAs) of biopolymers so far. Therefore, biopolymers have still a long way to go to convince the scientific community and the public that they can form a reliable alternative of polymers or plastics derived from fossil fuel resources.

Several of the commercial products mentioned in the manuscript and the accompanying tables are not anymore available in the market (obsolete). However, since these products are used to exemplify certain aspects of the cited patents, they were kept in the text.

The recycling of natural rubber, the most well known biopolymer, has already been analyzed and reviewed extensively in the past, and will not form part of this book.

One of the most striking results of this survey is the excessively large number of Japanese patent applications related to the waste treatment of biodegradable biopolymers. Actually, Japan has the highest number of patent applications worldwide relating to the waste treatment of biopolymers (66% of all patents). In spite of the large number of patents owned by Japanese companies, only two non-Japanese companies are actively involved on a large scale with the recycling of biopolymers or bioplastics; namely NatureWorks in the USA and Galactic S.A in Europe. However, in view of the large number of patent applications on the recycling of biopolymers future commercial implementation would be expected.

To the best of the author’s knowledge there are no books with a similar subject in the market. Useful books, but with a different scope and partial coverage, are the following:

-Handbook of Biodegradable Polymers Handbook of Biodegradable Polymers, 2005, Bastioli, C. (Ed), Smithers Rapra Technology, ISBN: 1859573894.

-Engineering Biopolymers - Markets, Manufacturing, Properties and Applications, 2011, Endres H. J., Siebert-Raths A., Hanser Publications, ISBN: 9781569904619.

-Biodegradable Plastics and Polymers, NIIR board, ISBN: 8178330350.

-Bioplastics In The Waste Stream (CD, online), 2012, iSmithers Rapra Publishing, 2012, ISBN: 9781847359452.

My sincere appreciation goes to Frank Hellwig, Associate Acquisitions Editor and Sina Ebnesajjad, Series Editor of the Plastics Design Library of Elsevier for their continuous support and commitment throughout all stages of production of this book.

For Supporting materials and web links to patents, please visit the companion website: http://booksite.elsevier.com/9781455731459

Rijswijk

Dr. Michael Niaounakis

Abbreviations of Biopolymers

1

Introduction to Biopolymers

Outline

1.1 Rationale for Use of Biopolymers

1.2 Types of Biopolymers

1.3 Polyesters

1.3.1 Poly(hydroxy acid)s

1.3.1.1 Poly(α-hydroxyalkanoic acid)s

1.3.1.2 Poly(β-, γ-, δ-hydroxyalkanoate)s (PHAs)

1.3.1.3 Poly(ω-hydroxyalkanoate)s

1.3.2 Poly(alkylene dicarboxylate)s

1.3.2.1 Aliphatic (co)polyesters

1.3.2.2 Aliphatic-aromatic copolyesters

1.3.2.3 Aromatic polyesters (bio-based)

1.4 Poly(ether-ester)s

1.5 Aliphatic Polycarbonates

1.6 Polyamides

1.6.1 Polycondensation of Diamines and Dicarboxylic Acids

1.6.2 Polycondensation of ω-Amino Carboxylic Acids or Lactams

1.6.3 Poly(α-amino acid)s

1.7 Poly(ester amide)s

1.8 Poly(ether amide)s

1.9 Polyurethanes (Bio-Based PUs)

1.10 Polysaccharides

1.11 Vinyl Polymers

1.12 Diene Polymers

1.13 Other Biodegradable Polymers

1.14 Biopolymer Compositions

1.14.1 Blends

1.14.2 Additives and Modifiers

1.15 Biodegradable Biopolymer Additives

1.16 Sources of Biopolymers

1.17 Applications and Parts

1.17.1 Service Packaging

1.17.2 Food Services

1.17.3 Agriculture/Forestry/Horticulture

1.17.4 Consumer Electronics

1.17.5 Automotive Industry

1.17.6 Textiles/Fibers

1.17.7 Medical and Pharmaceutical Sectors

1.17.8 Cosmetics

1.17.9 Outdoor Sports

1.17.10 Building/Construction Industry

1.17.11 Other Applications of Biopolymers

1.18 Sources of Scrap and Waste Biopolymers

References

1.1 Rationale for Use of Biopolymers

One of the fastest-growing materials sectors in the last several years has been the production of polymers from renewable resources. Their development is fueled by the potential these polymers hold to replace fossil fuel-based polymers. The main reasons for this drive can be summarized as follows: (1) limited fossil fuel resources; (2) pricing volatility of fossil fuel; (3) contribution of fossil fuel as a feedstock to climate change; (4) its occasional role as a political weapon; and (5) its association with the waste disposal problem created by the fossil fuel-derived polymers.

Polymers derived from renewable resources draw attention as environment-friendly resins because they are produced without relying on fossil fuel resources. In addition, the plants which provide the raw materials for these polymers absorb carbon dioxide as they grow, while the polymers themselves emit smaller quantities of CO2 when they are disposed of with an incinerator. The polymers that are based on renewable raw materials, as well as the polymers that are produced by biological routes, are generally biodegradable. The bio-based polymers, however, do not necessarily need to be biodegradable. This means that polymers that contribute to the protection of the environment include not only the bio-based polymers that are not biodegradable, but also biodegradable polymers. For this reason, the terms environmental polymer, enviropolymer, and biopolymer were coined for the sake of convenience in order to give a generic name to the bio-based polymers that are not biodegradable, and to the biodegradable polymers (including fossil fuel-based and bio-based polymers; see Chapter 2: Definitions and Assessment of (Bio)-degradation; Section 2.1: Define the Terms).

The main property that distinguishes biopolymers from fossil fuel-derived polymers is their sustainability, especially when combined with biodegradability. Biodegradable biopolymers from renewable resources have been synthesized to provide alternatives to fossil fuel-based polymers. They are often synthesized from starch, sugar, natural fibers, or other organic biodegradable components in varying compositions. The biopolymers are degraded by exposure to bacteria in soil, compost, or marine sediment. When the biodegradable biopolymers are subjected to waste disposal by utilizing their characteristic of being degradable by the bacteria in the ground, it significantly reduces emission of CO2 compared with conventional incineration. Therefore, attention is drawn to the use of biodegradable biopolymers from the viewpoint of global warming prevention. In recent years, with the critical situation of the global environment worsening due to global warming, the construction of systems with sustainable use of materials has been accelerated from the viewpoint of effectively using limited carbon resources and conserving limited energy resources. The Kyoto protocol, together with the desire to reduce society’s dependence on imported crude oil, has directed researchers’ efforts toward the use of biomass as a source of energy and of commodity chemicals. Furthermore, the cost of petroleum feedstocks has risen dramatically and there is a rising consumer interest in using green (or renewable resources) as the basis for consumer products.

Biodegradable biopolymers offer promise in solving the problem of conventional polymer disposal. In principle, it is not necessary to collect articles made of biodegradable biopolymers after the end of their useful life because they can be left to biodegrade in the environment. They offer a lot of advantages, such as increased soil fertility, low accumulation of bulky plastic materials in the environment, and reduction in the cost of waste management. But there have been several obstacles so far. Depending on the type and ratios of the components in biodegradable biopolymers, and depending on the environment where biodegradable biopolymers are disposed of, the rate of biodegradation may be less than desired. Another obstacle is that as the thickness of the product containing biodegradable biopolymer increases, its biodegradability property is diminished. A greater problem still is that many biopolymers have inferior properties, and it is often necessary to either blend them with other polymers or to compound them with various additives. As a result, many biopolymer blends or composites do not have uniform mechanical properties. Also, most known biodegradable polymers are aliphatic polyesters that have low softening temperatures (Tm), which prevents their use in a variety of fields.

In spite of several setbacks, biodegradable polymers are moving into the mainstream because conventional polymers are nondegradable and they exhaust fossil fuel sources. However, biopolymers still face a number of challenges, including cost reduction, wider availability, the need to improve their thermomechanical and barrier properties, speed of biodegradability, and availability and optimization of composting processes. As the demand for biopolymers increases, it is expected that their production capacity will expand and their prices will fall, and eventually, a denser network of industrial composting facilities will be created. But the ultimate issue is whether the performance properties and processability of biopolymers will ever be able to compete with the nonrenewable polymers.

1.2 Types of Biopolymers

Biopolymers are classified in several different ways at different scales. As explained in Chapter 2: Definitions and Assessment of (Bio)degradation; Section 2.1: Define the Terms, biopolymers can be divided into two broad groups, namely biodegradable and non-biodegradable, and alternatively, into bio-based and non-bio-based biopolymers.

On the basis of their polymer backbone, biopolymers can be classified roughly into the following groups, each of which is subdivided into several subgroups (this list is not exhaustive):

Polyesters

Poly(hydroxy acid)s top the list, and they include biopolymers such as the following:

• Poly(α-hydroxyalkanoic acid)s

• Polylactide (PLA, PLLA, PDLA)

• Polyglycolide (PGA)

• Poly(lactide-co-glycolide) (PLGA)

• Poly(tetramethyl glycolide) (PTMG)

• Poly(glycolide-co-trimethylene carbonate) (PGA/PTMC)

• Poly(2-hydroxybutyrate) (P2HB)

• α-type polymalic acid (α-PMA)

• Poly(β-, γ-, δ-hydroxyalkanoate)s (PHAs)

• Poly(3-hydroxypropionate (P3HP or PHP)

• Poly(3-hydroxybutyrate (P3HB or PHB)

• Poly(3-hydroxyvalerate) (P3HV or PHV)

• Poly(3-hydroxyhexanoate) (P3HH or PHH)

• Poly(3-hydroxyheptanoate) (P3HHp or PHHp)

• Poly(3-hydroxyoctanoate) (P3HO or PHO)

• Poly(3-hydroxynonanoate) (P3HN or PHN)

• Poly(3-hydroxydecanoate) (P3HD or PHD)

• Poly(4-hydroxypropionate (P4HP)

• Poly(4-hydroxybutyrate) (P4HB)

• Poly(4-hydroxyvalerate) (P4HV)

• Poly(3-hydroxybutyrate-co-hydroxypropionate) (PHBHP)

• Poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (P3HB/P3HV or PHB/PHV or PHBHx)

• Poly(3-hydroxybutyrate-co-3-hydroxyoctanoate) (P3HB/3HO or PHBO)

• Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (P3HB/P3HV or PHBHV)

• Poly(3-hydroxyoctanoate-co-3-hydroxyhexanoate) (P3HO/3HH or PHO/HH)

• Poly(3-hydroxybutyrate-co-3-hydroxydecanoate) (PHBHD)

• Poly(3-hydroxybutyrate-co-4-hydroxybutyrate) (P3HB/P4HB)

• β-type polymalic acid (β-PMA)

• Poly(5-hydroxyvalerate) (P5HV)

• Poly(ω-hydroxyalkanoate)s

• Poly(β-propiolactone) (β-PPL)

• Poly(β-butyrolactone) (β-PBL)

• Poly(ε-caprolactone) (PCL)

• Poly(alkylene dicarboxylate)s

• Poly(ethylene succinate) (PES)

• Poly(propylene succinate) (PPS)

• Poly(butylene succinate) (PBS)

• Poly(tetramethylene succinate) (PTeMS)

• Poly(ethylene adipate) (PEA)

• Poly(butylene adipate) (PBA)

• Poly(tetramethylene adipate) (PTA)

• Poly(hexamethylene adipate)

• Poly(ethylene succinate-co-adipate) (PESA)

• Poly(butylene succinate-co-adipate) (PBSA)

• Poly(butylene pimelate) (PBP)

• Poly(hexamethylene malonate)

• Poly(ethylene diethyl glutarate)

• Poly(tetramethylene glutarate)

• Poly(hexamethylene glutarate)

• Poly(hexamethylene diethyl glutarate)

• Poly(ethylene azelate) (PEAz)

• Poly(ethylene sebacate) (PESE)

• Poly(butylene sebacate) (PBSE)

• Poly(tetramethylene sebacate) (PTSE)

• Poly(hexamethylene sebacate) (PHSE)

• Poly(ethylene decamethylate) (PEDe)

• Poly(ethylene suberate) (PESu)

• Polyoxalate [poly(ethylene oxalate) (PEOx)]

• Poly(propylene fumarate) (PPF)

• Aliphatic-aromatic copolyesters

• Poly(butylene adipate-co-terephthalate) (PBAT)

• Poly(butylene succinate-co-terephthalate) (PBST)

• Poly(tetramethylene glutarate-co-terephthalate-co-diglycolate)

• Poly(tetramethylene glutarate-co-terephthalate)

• Poly(ethylene glutarate-co-terephthalate)

• Poly(tetramethylene adipate-co-terephthalate) (PTeMAT)

• Poly(tetramethylene succinate-co-terephthalate)

• Poly(tetramethylene-co-ethylene glutarate-co-terephthalate)

• Aromatic (co)polyesters

• Poly(ethylene terephthalate) (bio-based PET)

• Poly(ethylene furanoate) (PEF)

• Poly(trimethylene terephthalate) (bio-based PTT)

Poly(ether-ester)s

• Polydioxanone (PDO or PDS)

Polycarbonates, aliphatic

• Poly(ethylene carbonate) (PEC)

• Poly(propylene carbonate) (PPC)

• Poly(trimethylene carbonate) (PTMC)

• Poly(butylene carbonate) (PBC)

• Poly(tetramethylene carbonate) (PTeMC)

• Poly(cyclohexene carbonate) (PCHC)

• Poly(propylene carbonate)/poly(cyclohexene carbonate) (PPC/PCHC)

• Poly[(tetramethylene succinate)-co-(tetramethylene carbonate)] (PTMS/PTeMC)

• Poly(glycolide-co-trimethylene carbonate) (PGA/PTMC)

Polyamides

• By polycondensation of diamines and dicarboxylic acids:

• Polyamide 1010 (PA 1010)

• Polyamide 1012 (PA 1012)

• Polyamide 410 (PA 410)

• Polyamide 610 (PA 610)

• Polyphthalamides (PPA)

• By polycondensation of ω-amino carboxylic acids or lactams:

• Polyamide 11 (PA 11)

• Poly(α-amino acid)s

• Poly(γ-glutamic acid) (γ-PGA)

• Poly(α-aspartic acid)

• ε-Poly(L-lysine) (ε-PL)

• Polypeptides (collagen, casein, fibrin, gelatin)

• Proteins

Poly(ester amide)s

• Poly(butylene adipate-co-caproamide)

• Hyperbranched poly(ester amide)s

Polyurethanes (bio-based PU)

• Poly(ester urethane)s

• Poly(ether urethane)s

Polysaccharides

• Cellulose derivatives

• Methyl cellulose

• Ethyl cellulose

• Propyl cellulose

• Hydroxyethyl cellulose

• Carboxymethyl cellulose

• Hydroxypropyl cellulose

• Cellulose acetate (CA)

• Cellulose acetate butyrate (CAB)

• Cellulose acetate propionate (CAP)

• Cellulose nitrate (CN)

• Cellulose-chitosan

• Starch

• Lignin

• Chitin, chitosan

Vinyl Polymers

• Polyolefins (bio-based polyethylene, PE, LDPE, HDPE; bio-based polypropylene, PP)

• Poly(vinyl chloride) (bio-based PVC)

• Poly(vinyl alcohol) (PVOH)

Other Biodegradable Polymers

• Polyorthoesters I, II, III, IV (POE)

• Polyanhydrides

• Poly(carboxyphenoxy hexane-sebacic acid)

• Poly(fumaric acid-sebacic acid)

• Poly(imide-sebacic acid)

• Poly(imide-carboxyphenoxy hexane)

• Polyphosphazenes (PPHOSs)

1.3 Polyesters

Polyesters, especially the aliphatic ones, are the most extensively studied class of biopolymers [1]. They can be classified into two groups according to the bonding of the constituent monomers [2]. The first group consists of the poly(hydroxy acid)s. These are polyesters synthesized from hydroxy acids (hydroxycarboxylic acids), HO-R-COOH, or by ring-opening polymerization of cyclic monomers, –R-COO–. The second group consists of the poly(alkylene dicarboxylate)s. These are polyesters prepared by polycondensation of diols and dicarboxylic acids.

1.3.1 Poly(hydroxy acid)s

A series of hydroxy acids are the hydroxyalkanoic acids, and the corresponding polymers are subdivided into three categories: poly(α-hydroxyalkanoic acid)s, poly(β-hydroxyalkanoic acid)s and poly(ω-hydroxyalkanoate)s. The term polyhydroxyalkanoate is normally used for poly(hydroxyalkanoic acid)s derived from β-hydroxyalkanoic acids, and in certain cases, even γ-, δ-, and ε-hydroxyalkanoic acids.

1.3.1.1 Poly(α-hydroxyalkanoic acid)s

Poly(α-hydroxyalkanoic acid)s are poly(α-ester)s derived from α-hydroxyalkanoic acids (see Scheme 1.1). A list of common α-hydroxyalkanoic acids is shown in Table 1.1.

Scheme 1.1 α-Hydroxyalkanoic acid.

Table 1.1

List of α-hydroxyalkanoic acids

Common α-hydroxyalkanoic acids include lactic acid, glycolic acid, tartaric acid, malic acid, mandelic acid, benzylic acid, valeric acid, α-hydroxybutyric acid, α-hydroxyoctanoic acid, α-hydroxystearic acid, and mixtures thereof. The most used α-hydroxyalkanoic acids are lactic acid, glycolic acid, and mixtures thereof; the corresponding polymers, polylactide (PLA) and polyglycolide (PGA), and copolymers thereof, have been known for years.

Polylactide (PLA)

Polylactide or polylactic acid (PLA) is a linear aliphatic poly(α-ester) or α-hydroxyalkanoic acid-derived polyester (see Scheme 1.2).

Scheme 1.2 Polylactide (PLA).

PLA is obtainable primarily by the ionic polymerization of lactide, a ring closure of two lactic acid molecules. At temperatures between 140° and 180°C and under the action of catalytic tin compounds (such as tin oxide), a ring-opening polymerization takes place. Lactide itself can be made through lactic acid fermentation from renewable resources such as starch by means of various bacteria. PLA can also be produced directly from lactic acid by polycondensation. However, this process yields low molecular weight polymers, and the disposal of the solvent is a problem in the industrial production. Various procedures for synthesizing, purifying, and polymerizing lactide are disclosed in US4057537 A (1977, GULF OIL CORP), EP0261572 A1 (1988, BOEHRINGER INGELHEIM KG; BOEHRINGER INGELHEIM INT) and described in the literature [3–5].

There are two optically active forms of lactic acid: L-lactic acid and D-lactic acid. Consequently, the lactide, the cyclic dimer of lactic acid, may occur in three isomeric forms depending on whether it consists of: (1) two L-lactic acid molecules, L-lactide; (2) two D-lactic acid molecules, D-lactide; or (3) one L-lactic acid molecule and one D-lactic acid molecule, meso-lactide. The meso-lactide is characterized by a melting point (Tm) of around 50°C, whereas the melting point of the L- and D-lactide isomers is 97°C. An equimolar mixture of the L- and D-lactides results in LD-lactide (rac-lactide) (see Scheme 1.3).

Scheme 1.3 Stereoisomeric forms of lactide.

Polylactide resins are classified into poly(L-lactide) (PLLA), poly(D-lactide) (PDLA), syndiotactic poly(D,L-lactide) (syndiotactic PDLLA), attactic poly(D,L-lactide) (attactic PDLLA), and copolymers with other polymers, depending on the type of constitutive monomer (see Scheme 1.4). There is also another form of PLA known as isotactic stereocomplex, prepared from rac-lactide using a racemic catalyst (isopropoxide), which has the added advantage of possessing a melting point approximately 50°C higher than the homochiral polymers [6]. The mechanical properties of all these types of PLA are as different as their degradation times [7]. Thus, a regular PLLA is a hard, transparent polymer; it has a Tm of 165–185°C, a glass transition temperature (Tg) of 53–63°C, and a crystallization temperature (Tc) of 100–120°C. On the other hand, attactic PDLLA has no melting point, a Tg around 55°C, and it shows much lower tensile strength [8].

Scheme 1.4 Stereoisomeric forms of polylactide (PLA).

The properties of PLA depend primarily on the molecular mass, the degree of crystallinity, and possibly the proportion of co-monomers. A higher molecular mass raises Tg, as well as Tm, tensile strength, elastic modulus, and lowers the strain after fracture. Due to the CH3 side group (see Scheme 1.2), the material has water-repellent or hydrophobic behavior. PLA is soluble in many organic solvents, such as dichloromethane or the like. PLA has higher transparency than other biodegradable polymers, and is superior in weather resistance and workability.

PLA has low melt viscosity, which is required for the shaping of a molding. PLA is, however, slow in the crystallization rate with long molding cycles and has poor gas properties; furthermore, it has inferior thermal resistance and mechanical characteristics (toughness, impact resistance, and the like) compared with those of existing synthetic resin molded articles. To solve these problems, many countermeasures are used in forming PLA, including blending PLA with other polymers, and compounding various kinds of substances as filler; thus, PLA products have been entering practical applications.

PLA is gaining a lot of interest due to its biodegradability, biocompatibility, and renewable resource-based origin. It can be said that PLA is a low environment load polymer that does not cause a direct increase in the total amount of carbon dioxide gas, even if the polymer is finally biodegraded or burned up. The biodegradability of PLA, however, has both positive and negative aspects. The positive aspects of PLA are its ability to form non-hazardous products when PLA polymers or articles are discarded or composted after completing their useful life, and its slow degradation period (several weeks up to about one year), which is advantageous for some applications as it leads to a relatively good shelf life. The negative aspects are that the thermal degradation of PLA during processing causes deterioration of properties, and that the degradation rate of PLA is still low as compared to the waste accumulation rate, which means that a large amount of PLA left untreated outdoors may cause a new environmental problem. Thus, the same properties that make PLA polymers desirable as replacements for nondegradable fossil fuel-based polymers also create undesirable effects which must be overcome. PLA has a considerably lower biodegradability than poly(ε-caprolactone) (PCL) or poly(3-hydroxybutyrate) (PHB). PLA is the most common biopolymer currently on the market. As such, it has a variety of brand names associated with it (see Table 1.2).

Table 1.2

Commercial α-hydroxycarboxylic acid-derived polyesters

Abbreviations: PGA, Polyglycolide; PGCL, Poly(glycolide-co-caprolactone); PLA, Polylactide; PLCL, Poly(lactide-co-caprolactone); PLGA, Poly(lactide-co-glycolide).

†VYLOECOL® is made from lactides supplied by Purac. They are marketed under the brand name PURALACT™.

Polyglycolide (PGA)

Polyglycolide (PGA) is the simplest linear aliphatic polyester (see Scheme 1.5). Glycolide monomer is synthesized from the dimerization of glycolic acid. Ring-opening polymerization yields high molecular weight materials, with approximately 1–3% residual monomer present. PGA is highly crystalline (45–55%), with a high Tm (220–225°C) and a Tg of 35–40°C [9]. Because of its high degree of crystallinity, it is not soluble in most organic solvents, the exceptions being highly fluorinated organics such as hexafluoroisopropanol.

Scheme 1.5 Polyglycolide (PGA).

PGA has an extremely high gas-barrier property, as high as ca. 3 times or higher (i.e., ca. 1/3 or lower in terms of an oxygen transmission coefficient) than that of ethylene-vinyl alcohol copolymer (PEVOH), which is a representative gas-barrier resin used heretofore. This means that a bottle (especially one made of PET) with a remarkably improved gas-barrier property can be obtained by including a thin layer of PGA in addition to the principal resin layer. Accordingly, it becomes possible to effectively prevent the degradation of contents due to oxidation or poorer quality due to dissipation of carbon dioxide gas. Furthermore, PGA has a substantial hydrolyzability with alkaline washing liquid, water (particularly warmed water), or acidic water. In contrast, PLA does not exhibit gas-barrier properties like that of PGA, and can only show a slower hydrolyzation speed with alkaline water, water, or acidic water (WO03097468 A1, 2003, KUREHA CHEM IND CO LTD). Fibers from PGA exhibit high strength and modulus and are too stiff to be used as sutures except in the form of braided material. Sutures of PGA lose about 50% of their strength after two weeks and 100% at four weeks, and are completely absorbed in 4–6 months. Glycolide has been copolymerized with other monomers to reduce the stiffness of the resulting fibers. PGA can be utilized as a packaging material (e.g., lightweight PET bottles) as well as for oil recovery and other industrial and medical applications.

Poly(lactide-co-glycolide) (PLGA)

Poly(lactide-co-glycolide) (PLGA) is a copolymer of hydrophobic PLA and hydrophilic PGA (see Scheme 1.6). L-lactide and D,L-lactide have been used for copolymerization with glycolide. Amorphous polymers are obtained for a 25 lactide/75 glycolide monomer ratio. A copolymer with a monomer ratio of 80 lactide/20 glycolide is semicrystalline. When the ratio of monomer lactide/glycolide increases, the degradation rate of the copolymer decreases [1].

Scheme 1.6 Poly(lactide-co-glycolide) (PLGA).

PLGA is useful in drug delivery and tissue regeneration applications since it degrades into harmless substances. Since polymers of lactic acid and glycolic acid and their copolymers (PLGA) degrade quickly in the body into nontoxic products, PLGA is used for biodegradable sutures and can potentially be used in implantable screws, intravascular stents, pins, drug delivery devices, and as a temporary scaffold for tissue and bone repair. Additionally, PLGA has good mechanical properties that improve the structural integrity of such devices. However, since PLGA degrades completely by bulk erosion, it loses more than 50% of its mechanical strength in less than two months, which can lead to uncontrollable drug release rates and biocompatibility problems; this is probably due to an accumulation of lactic and glycolic acids during degradation (US6077916 A, 2000, PENN STATE RES FOUND).

1.3.1.2 Poly(β-, γ-, δ-hydroxyalkanoate)s (PHAs)

Polyhydroxyalkanoates (PHAs) are polyesters in which the hydroxyl group and the carboxyl group of hydroxyalkanoic acids are linked via oxoester bonds. The general formula of polyhydroxyalkanoates is given in Scheme 1.7. The hydroxyalkanoic acids are distinguished mainly by the position of the hydroxyl group in relation to the carboxyl group (see Scheme 1.8a and b), by the length of the side-alkyl chain, by a large variety of substituents in the side chains, and by one additional methyl group at carbon atoms between the hydroxyl and the carboxyl groups [10]. Unlike polymers derived from α-hydroxyalkanoic acids, like PLA and PGA, the polyhydroxyalkanoates are normally comprised of β-hydroxyalkanoic acids, and in certain cases, even γ- and δ-hydroxyalkanoic acids.

Scheme 1.7 General formula of polyhydroxyalkanoates; wherein m ≥ 1, R = H, (un)substituted alkyl.

Scheme 1.8a β-Hydroxyalkanoic acid.

Scheme 1.8b γ-Hydroxyalkanoic acid.

To date, more than 150 hydroxyalkanoic acids have been detected as constituents in bacterial PHAs; these constituents are produced by microorganisms grown on carbon substrates containing different types of chemical structures [10–12]. Beside linear and branched β-, γ-, δ-, and ε-hydroxyalkanoates, various constituents such as PHAs containing halogenated or aromatic side chains have been described [13,14]. A list of β-, γ-, and δ-hydroxyalkanoic acids is given in Table 1.3.

Table 1.3

List of β-, γ- and δ-hydroxycarboxylic acids

PHAs are commercially produced by several bacteria as intercellular carbon and energy storage materials [15]. PHAs may constitute up to 90% of the dry cell weight of bacteria, and are found as discrete granules inside the bacterial cells. Produced naturally by soil bacteria, PHAs are degraded upon subsequent exposure to these same bacteria in soil, compost, or marine sediment. Biodegradation begins when microorganisms start growing on the surface of PHA and secrete enzymes that break down the biopolymer into hydroxy acid monomeric units. The hydroxy acids are then taken up by the microorganisms and used as carbon sources for growth. The monomers and polymers can also be produced chemically.

In addition to commercial use as a biodegradable replacement for synthetic commodity resins, PHAs have been extensively studied for use in biomedical applications. These studies range from potential applications in controlled release, to use in formulation of tablets, surgical sutures, wound dressings, lubricating powders, blood vessels, tissue scaffolds, surgical implants to join tubular body parts, bone fracture fixation plates, and other orthopedic uses (WO9932536 A1, 1999, METABOLIX INC).

Because of their great compositional diversity, PHAs with a range of physical properties can be produced [16]. There are currently several commercially available PHAs, including poly-3-hydroxybutyrate (PHB), poly-(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), poly(3-hydroxybutyrate-co-4-hydroxybutyrate) (P3HB4HB), and poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBHx), which are derived from bacterial fermentations (Table 1.4).

Table 1.4

Commercial polyhydroxyalkanoates (PHAs)

Abbreviations: PHB, Polyhydroxybutyrate; PHBV, Poly(3-hydroxybutyrate-co-3-hydroxy valerate); P3HB4HB, Poly(3-hydroxybutyrate-co-4-hydroxybutyrate); PHBHx, Poly(3-hydroxybutyrate-co-3-hydroxyhexanoate).

¹The P and F versions refer to general purpose and food contact applications, respectively.

²On 12 January 2012 Metabolix announced that Archer Daniels Midland Company (ADM) had given notice of termination of the Telles, LLC joint venture for PHA bioplastics. Telles was established as a joint venture between Metabolix and ADM in July 2006. The joint venture sold PHA-based bioplastics, including Mirel and Mvera, in the US, Europe and other countries.

³Meredian, Inc. bought Nodax PHA technology from Procter & Gamble Co.

⁴Monsanto’s rights to BIOPOL® were sold to the American company Metabolix in 2001.

This class of polyesters is attractive as a potential alternative to conventional fossil fuel-based polymers. PHAs can be processed by traditional polymer techniques for use in an enormous variety of applications, including consumer packaging, disposable diaper linings, garbage bags, and food and medical products [15,17].

Polyhydroxybutyrate (PHB or P3HB)

Polyhydroxybutyrate (PHB or P3HB) is synthesized and stored within cells as an energy source for various microorganisms [18,19]. PHB can be extracted from the microorganisms. Example techniques are disclosed in AU5560680 A (1980, ICI PLC) and EP0046335 A2 (1982, ICI PLC) (Scheme 1.9).

Scheme 1.9 Poly(3-hydroxybutyrate) (PHB or P3HB).

PHB is a homopolymer having stereoregular structure with high crystallinity. The high crystallinity leads to a rather stiff and brittle material. PHB has low melt viscosity and a narrow processing window. Its inherent brittleness and thermal instability during melt processing impedes its commercial applications [20]. Plasticization of PHB or addition of processing additives (e.g., nucleants) is often practiced in order to overcome its brittleness (see Section 1.14.2: Additives and Modifiers). The commercial products of PHB are outlined in Table 1.4.

PHB is used in the manufacture of body-waste bags, whether alone or as a coating on a water-soluble polymer, because of its good impermeability to water and vapor (US4372311 A, 1983, UNION CARBIDE CORP). Films or coatings of PHB may be made by solution-coating techniques or by melt extrusion. Upon degradation of PHB, the water-soluble polymer can dissolve, thus avoiding obstruction of sewage pipes and sewage treatment plants. However, it is claimed that the degradation rate of PHB is often too slow to avoid the formation of the aforementioned obstructions (AU3521984 A, 1985, ICI PLC). The rate of degradation can be markedly increased by modification of the pH of the bag contents (see Chapter 7: Degradability on Demand; Section 7.3.4: Compounds Which Can Initiate and/or Propagate Depolymerization).

Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV)

Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) is a copolymer in which 3-hydroxyvalerate (HV) units are incorporated in the PHB backbone during the fermentation process (see Scheme 1.10). Microbiologically produced PHBV can be made by the techniques described in EP0052459 A1 (1982) and EP0069497 A2 (1983, ICI PLC). The use of copolymers (e.g., containing 10 to 25, and particularly 15 to 20 mol% of HV units) may in some cases be advantageous for lowering the modulus of the PHB since bags made from a film of such copolymers would be less likely to make rustling noises upon movement by the wearer.

Scheme 1.10 Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV).

PHBV has improved flexibility and toughness and a lower processing temperature than PHB. Presently, PHBV with an HV content below 15 mol% is commercially available, while large-scale production of PHBV with higher HV content is presently not commercially viable due to the surprisingly high production cost [21]. The available PHBV (with an HV content of less than 15 mol%) has a low toughness and elongation at break. PHBV has achieved a certain economic importance because of its polypropylene-like properties. Its commercial products are outlined in Table 1.4. They have the potential to replace polypropylene (PP) and other conventional fossil-based polymers if the PHB and PHBV-based materials can be developed with a balance of properties such as stiffness and toughness. PHB and PHBV often have unsatisfactory properties. PHB tends to be thermally unstable, while PHB and PHBV often have slow crystallization rates and flow properties that make processing difficult. For example, PHBV remains tacky for long periods of time, and may stick to itself when being processed into films.

Commercially available PHB and PHBV represent only a small component of the property sets available to PHAs. For example, the elongation at break of PHB and PHBV ranges from around 4 to 42%, whereas the same property for poly-4-hydroxybutyrate (P4HB) is about 1000%. Similarly, the values of Young’s modulus and tensile strength for PHB and PHBV are 3.5 to 0.5 GPa and 40 to 16 MPa (for increasing HV content to 25 mol%), respectively, compared to 149 MPa and 104 MPa, respectively, for P4HB [22].

In addition to finding commercial use as a biodegradable replacement for synthetic commodity resins, PHB and PHBV have been extensively studied for use in biomedical applications. These studies range from potential uses in controlled drug delivery [23,24], to use in formulation of tablets, surgical sutures, wound dressings, lubricating powders, blood vessels, tissue scaffolds, surgical implants to join tubular body parts, bone fracture fixation plates, and other orthopedic uses, as described in WO9851812 A2 (1998, METABOLIX INC). PHB and PHBV are also used for preparation of a porous, bioresorbable flexible sheet for tissue separation and stimulation of tissue regeneration in injured soft tissue as disclosed in EP0349505 A2 (1990, ASTRA MEDITEC AB).

Poly(3-hydroxybutyrate-co-4-hydroxybutyrate) (P3HB4HB)

Poly(3-hydroxybutyrate-co-4-hydroxybutyrate) (P3HB4HB) was first found in 1988 from Ralstonia eutropha cultivated with 4-hydroxybutyric or 4-chlorobutyric acid as carbon sources. The incorporation of 4-hydroxybutyrate (4HB) units into PHB (or P3HB) improves the material application potential, and the copolymer shows a wide range of physical properties ranging from highly crystalline polymer to elastic rubber, depending on the polymer composition (see Scheme 1.11). Generally, carbon sources structurally related to 4HB are required to generate 4HB-containing PHA, such as 4-hydroxybutyric acid, γ-butyrolactone, and 1,4-butanediol. However, these carbon sources are much more