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Biodegradable

Polymers

Market Report

David K. Platt

Biodegradable Polymers Market Report David K. Platt A Smithers Group Company ©PlasBio ©PlasBio Inc. Inc.

A Smithers Group Company

©PlasBio©PlasBio Inc.Inc. (www.plasbio.com)(www.plasbio.com)

Biodegradable Polymers

Market Report

David K. Platt

Biodegradable Polymers Market Report David K. Platt Smithers Rapra Limited A wholly owned subsidiary of The

Smithers Rapra Limited A wholly owned subsidiary of The Smithers Group

Shawbury, Shrewsbury, Shropshire, SY4 4NR, United Kingdom Telephone: +44 (0)1939 250383 Fax: +44 (0)1939 251118 http://www.rapra.net

Published in 2006 by

Smithers Rapra Limited

Shawbury, Shrewsbury, Shropshire, SY4 4NR, UK

©2006, Smithers Rapra Limited

All rights reserved. Except as permitted under current legislation no part of this publication may be photocopied, reproduced or distributed in any form or by any means or stored in a database or retrieval system, without the prior permission from the copyright holder.

A catalogue record for this book is available from the British Library.

Every effort has been made to contact copyright holders of any material reproduced within the text and the authors and publishers apologise if any have been overlooked.

ISBN: 1-85957-519-6

Typeset by Smithers Rapra Limited Cover printed by Telford Reprographics Limited, Telford, UK Printed and bound by Smithers Rapra Limited, Shrewsbury, UK

Contents

1. Introduction

1

1.1 Background

1

1.2 The Report

2

1.3 Methodology

3

1.4 About the Author

3

2. Executive Summary

5

2.1 Global Market Forecasts

5

2.2 Material Trends

6

2.3 Regional Trends

7

2.4 Market Trends

8

2.5 Competitive Trends

9

3. Overview of Biodegradable Polymers

11

3.1 Introduction

11

3.2 Definitions of Biodegradable Polymers

11

3.3 Mechanisms of Polymer Degradation

11

3.4 Measuring Biodegradability of Polymers

12

3.5 Factors Affecting Biodegradability

13

3.6 Biodegradable Polymer Classes

14

3.6.1 Naturally Biodegradable Polymers

15

3.6.2 Synthetic Biodegradable Polymers

15

3.6.3 Modified Naturally Biodegradable Polymers

15

3.7 Starch-Based Biodegradable Polymers

16

3.8 Polyhydroxyalkanoates

18

3.9 Polylactic Acid Polyesters

20

3.10 Synthetic Biodegradable Polymers

22

3.10.1 Polycaprolactone (PCL)

22

3.10.2 Polyglycolide (PGA)

23

3.10.3 Poly(dioxanone) (a polyether-ester)

23

3.10.4 Poly(lactide-co-glycolide)

23

Biodegradable Polymers

3.11

Processing Biodegradable Polymers

25

3.11.1 Introduction

25

3.11.2 Film Blowing and Casting

25

3.11.3 Injection Moulding

27

3.11.4 Blow Moulding

27

3.11.5 Injection Stretch Blow Moulding

28

3.11.6 Thermoforming

29

3.11.7 Fibre Spinning

30

4. The Global Biodegradable Polymers Market

31

4.1 Introduction

31

4.2 Market Drivers

31

 

4.2.1 Development of Framework Conditions

31

4.2.2 Development of a Composting Infrastructure

35

4.2.3 Pricing Trends

37

4.2.4 Growth in Pre-Packaged Food Sales

38

4.2.5 Consumer Preference for Sustainable Packaging

38

4.2.6 Product and Technology Development

39

4.3 Market Development and Structure

39

4.4 The Global Biodegradable Polymers Market Forecast

41

 

4.4.1 Western European Biodegradable Polymers Market Forecast

44

4.4.2 North American Biodegradable Polymers Market Forecast

46

4.4.3 Asia Pacific Biodegradable Polymers Market Forecast

48

5. The Starch-Based Biodegradable Polymer Market

57

5.1 Introduction

57

5.2 Applications Development

57

5.3 Market Drivers

59

5.4 Market Size and Forecast

60

5.5 Major Suppliers and their Products

61

 

5.5.1 Novamont

61

5.5.2 Rodenburg Biopolymers, BV

63

5.5.3 EarthShell Corporation

63

5.5.4 Stanelco Group

64

5.5.5 Grenidea Technologies

65

5.5.6 Biopolymer Technologies

65

5.5.7 NNZ BV

65

5.5.8 Plantic Technologies

66

Contents

6. The Polylactic Acid Biodegradable Polymers Market

67

6.1 Introduction

67

6.2 Applications Development

67

6.2.1 Rigid Packaging

68

6.2.2 Flexible Packaging

69

6.2.3 Blow Moulded Bottles

70

6.2.4 High Performance Applications

70

6.3 Market Drivers

70

6.3.1 Better Environmental Credentials

71

6.3.2 Stable Supply and More Competitive Prices

71

6.3.3 World’s First Greenhouse-Gas-Neutral Polymer

71

6.3.4 Replacement of Traditional Packaging Materials

72

6.3.5 Speciality Cards

72

6.3.6 Source Options

72

6.3.7 New Applications

73

6.3.8 Better Processing

73

6.4 Market Size and Forecast

74

6.5 Major Suppliers and their Products

75

7. The PHA Biodegradable Polymers Market

79

7.1 Introduction

79

7.2 Applications Development

81

7.2.1 Films

82

7.2.2 Flexible Packaging

82

7.2.3 Thermoformed Articles

82

7.2.4 Coated/Corrugated Paper

82

7.2.5 Synthetic Papers

83

7.2.6 Bioresorbable Medical Devices

83

7.2.7 Polymer Blends

83

7.3 Market Drivers

83

7.4 Market Size and Forecast

84

7.5 Suppliers and their Products

84

8. The Synthetic Biodegradable Polymers Market

87

8.1 Introduction

87

8.2 Applications Development

88

Biodegradable Polymers

8.3 Market Drivers

89

8.4 Market Size and Forecast

89

8.5 Suppliers and their Products

90

9. Market Opportunities for Biodegradable Polymers

93

9.1 Introduction

93

9.2 Packaging

93

9.2.1 Flexible Packaging

93

9.2.2 Rigid Packaging

94

9.2.3 Paper Coating

96

9.2.4 Loose-Fill Packaging

97

9.3 Bags and Sacks

97

9.4 Disposable Serviceware

97

9.5 Agriculture and Horticulture

98

9.6 Medical Devices

98

9.6.1 Sutures

98

9.6.2 Dental Devices

99

9.6.3 Orthopaedic Fixation Devices

99

9.6.4 Other Applications

99

9.7 Consumer Electronics Products

100

9.8 Automotive

100

9.9 Speciality Cards

101

9.10 Fibres

101

10. Profiles of Leading Biodegradable Plastics Converters

103

10.1 Alpha Packaging

103

10.2 Arkhe Planning

103

10.3 Arthur Blank & Company

104

10.4 Autobar Group

105

10.5 Bartling GmbH & Co. KG Kunststoffe

106

10.6 Bi-Ax International

106

10.7 BioBag International AS

107

10.8 Biosphere Industries Corporation

108

10.9 BIOTA Brands of America

108

Contents

10.10 Bomatic

109

10.11 Brenmar Company

109

10.12 Carolex SAS

110

10.13 Chien Fua Bio-Tech Industry Co.,

111

10.14 Coopbox Europe

111

10.15 Cortec Corporation

112

10.16 Earthcycle Packaging Ltd

113

10.17 Europackaging plc

114

10.18 Ex-Tech Plastics,

114

10.19 Fabri-Kal

115

10.20 Faerch Plast A/S

115

10.21 Farnell Packaging

116

10.22 Fortune Plastics

116

10.23 Good Flag Biotechnology Corporation

117

10.24 Grenidea Technologies Pte Ltd

118

10.25 The Heritage Bag Company

118

10.26 Huhtamäki Oy

119

10.27 IBEK Verpackungshandel GmbH

120

10.28 ILIP

121

10.29 Innovia Films BVBA

122

10.30 Liquid Container/Plaxicon

123

10.31 NNZ bv

123

10.32 Natura Verpackungs GmbH

124

10.33 NVYRO

125

10.34 Plastic Suppliers

126

10.35 RPC Group plc

127

10.36 Siamp-Cedap

128

10.37 Sidaplax

129

10.38 Signum NZ

129

10.39 Spartech Corp

130

10.40 Sunway Household

131

Biodegradable Polymers

10.41 Toray Industries

131

10.42 Toray Saehan

132

10.43 Treofan Group

133

10.44 Vertex Pacific Limited

134

10.45 Wei Mon Industry Co.

135

10.46 Wentus Kunststoff GmbH

136

10.47 Wilkinson Industries

137

11. Database of Major Biodegradable Polymer Suppliers

139

12. Glossary of Terms

145

13. Abbreviations and Acronyms

155

1

Introduction

1.1 Background

Biodegradable polymers have been around for almost a decade, but it has only been in the last two to three years that they have started to be produced on a commercial scale. Biodegradable polymers have already found acceptance in application areas such as food packaging, bags and sacks, loose- fill packaging agricultural film and many niche market applications. However, while they remain very much a niche product at the moment, there are signs that biodegradable polymers are ready to attack mass markets with a number of major suppliers such as NatureWorks LLC, Novamont and BASF, gearing up for large-scale production.

Biodegradable polymer demand is being driven by a number of important trends. In developed countries of the Western world, particularly in Western Europe, governments have implemented legislation to reduce the amount of municipal waste packaging being sent to landfill. Other options being pursued include mechanical recycling, incineration with energy recovery and composting. As these trends gather momentum, more favourable framework conditions for biodegradable plastics market development are slowly coming into place.

There is also a growing trend for brand owners and retailers to recognise the potential marketing benefits of ‘green’ or ‘sustainable’ packaging as consumers become more concerned about the development of sustainable technologies, reduction in CO 2 emissions and the conservation of the earth’s fossil resources. Several major world brands including Wal-Mart have been persuaded to switch from petrochemical-based plastics to biodegradable plastics in recent years.

Demand for biodegradable polymers is also benefiting from a narrowing in the price differential between biopolymers and petrochemical-based plastics over the last two years. Petrochemical- based plastic prices have gone up sharply due to a surge in crude oil prices and look like remaining at historically high levels for some time to come. At the same time, biopolymer prices have come down significantly in recent years due to better production techniques, better material sourcing by suppliers and higher production volumes. In 2006, certain starch-based and PLA biopolymers were competitive with standard thermoplastics such as PET.

This report uses the American Society for Testing and Materials (ASTM) definitions of biodegradable and compostable plastics.

• Biodegradable plastic: a biodegradable plastic is a degradable plastic in which the degradation results from the action of naturally occurring microorganisms such as bacteria, fungi and algae.

• Composting: composting is a managed process that controls the biological decomposition of biodegradable materials into a humus-like substance called compost; the aerobic and mesophilic and thermophilic degradation of organic matter to make compost; the transformation of biologically decomposable materials through a controlled process of bio-oxidation that proceeds through mesophilic and thermophilic phases and results in the production of carbon dioxide, water, minerals and stabilised organic matter (compost or humus).

Biodegradable Polymers

Biodegradable polymers and biopolymers can be produced by a wide variety of technologies, both from renewable resources of animal or plant origin, and from fossil resources. A number of different types are already available on the market.

Biodegradable polymers that are based on renewable resources include polyesters such as polylactic acid (PLA) and polyhydroxyalkanoate (PHA). Biodegradable polymers can also be made from extracts from plants and vegetables such as corn, maize, palm oil, soya and potatoes.

Biodegradable polymers can also be made from mineral oil based resources such as the aliphatic- aromatic co-polyester types. Mixtures of synthetic degradable polyesters and pure plant starch, known as starch blends, are also well-established products on the market.

Biodegradable polymers are similar in terms of their chemical structure to conventional thermoplastics such as polyethylene, polypropylene and polystyrene. They can be processed using standard polymer processing methods such as film extrusion, injection moulding and blow moulding.

While biodegradable polymers may be similar to petrochemical-based thermoplastics in terms of their structure, their chemical structure imbues them with technical properties that make them perform in different ways. For example, starch blends can produce film with better moisture barrier protection and higher clarity than some conventional plastics. PLA has a high water vapour transmission rate, which is beneficial for fresh food applications where it is important that the water vapour escapes quickly from the packaging. PLA also reduces fogging on the lid of the packaging.

1.2 The Report

The report starts with an overview of biodegradable polymers including an examination of the processes of biodegradation, classification of biodegradable polymers including their chemical structure, properties, and processing performance.

Section 4 examines the global market for biodegradable polymers by major geographic region, covering Western Europe, North America and Asia Pacific. Biodegradable polymer consumption by polymer type and end use market is presented for each region for the years 2000, 2005 and forecast for 2010.

The main body of the study (Chapters 5-8) is divided into four core sections based on biodegradable polymer types.

• Starch-based

• Polylactic acid (PLA)

• Polyhydroxyalkanoates (PHA)

• Synthetic biodegradable polymers such as aliphatic-aromatic co-polyesters

Each section contains an overview of key market drivers, analysis of world consumption by geographic region for the years 2000, 2005 and forecast for 2010, application developments and an analysis of the major suppliers and their products.

Chapter 9 examines the market opportunities for biodegradable plastics by end use market covering packaging, bags and sacks, disposable serviceware, agriculture and horticulture, medical devices, consumer electronics products, automotive, speciality cards and fibres.

Introduction

Finally, Chapter 10 examines around fifty major processors of biodegradable plastics and their products, including: BioBag International, Biosphere Industries, Bomatic, Coopbox, Cortec, Europackaging, Ex-Tech Plastics, The Heritage Bag Company, Huhtamäki, IBEK, Innovia Films, NNZ, natura Verpackungs, Plastic Suppliers, RPC Group, Toray and Treofan.

1.3 Methodology

The research for the report is based on various information sources including: the Rapra Polymer Library, trade press, Internet/company web sites, and interviews with some of the leading suppliers. The opinions expressed and the data presented are those of the author.

1.4 About the Author

David Platt graduated from the University of Nottingham with an Economics degree before completing an MBA at the University of Bradford. He joined a leading international market consultancy where he specialised in plastics sector research. He conducted a wide range of multi-client and single-client studies covering a wide range of materials, from standard thermoplastics, engineering and high performance polymers to conductive polymers and thermoplastic elastomers.

Now operating as a freelance consultant, he makes regular contributions to the European plastics trade press, and also works with leading plastics industry consultants.

Biodegradable Polymers

2 Executive Summary

2.1 Global Market Forecasts

The market for biodegradable polymers has shown strong growth during the last five years, albeit from a very small base. However, there are still only a handful of producers operating truly commercial scale production plants. The situation is slowly changing with a number of major plant expansions planned over the next few years.

The major classes of biopolymer, starch and starch blends, polylactic acid (PLA) and aliphatic- aromatic co-polyesters, are now being used in a wide variety of niche applications, particularly for manufacture of rigid and flexible packaging, bags and sacks and foodservice products. However, market volumes for biopolymers remain extremely low compared with standard petrochemical- based plastics. For example, in 2005, biopolymer consumption accounted for just 0.14% of total thermoplastics consumption in Western Europe.

In 2005, the global biodegradable plastics market tonnage is estimated at 94,800 tonnes (including loose-fill packaging) compared with 28,000 tonnes in 2000. In 2010, market tonnage is forecast to reach 214,400 tonnes, which represents a compound annual growth rate of 17.7% during the period 2005-2010. Excluding loose-fill packaging, which is a relatively more mature sector for biodegradable polymers, global market tonnage in 2005 is 71,700 tonnes and the compound annual growth rate for the period 2005-2010 is 20.3%.

Table 2.1 shows global consumption of biodegradable polymers by polymer type for the years 2000, 2005 and forecast for 2010.

Table 2.1 Global consumption of biodegradable polymers by polymer type, 2000, 2005 and forecast for 2010 (’000 tonnes)

 

2000

2005

2010

Starch

15.5

44.8

89.2

PLA

8.7

35.8

89.5

PHA

0

0.2

2.9

Synthetic

3.9

14.0

32.8

 

28.1

94.8

214.4

In 2005, starch-based materials were the largest class of biodegradable polymer with just over 47% of total market volumes. Loose-fill foam packaging accounts for more than a half of starch biopolymer volumes. Polylactic acid (PLA) is the second largest material class followed by synthetic aliphatic- aromatic co-polyesters. The PHA category is at an embryonic stage of market development with very low market tonnage at the moment.

Biodegradable Polymers

All classes of biodegradable polymers are projected to experience substantial growth during the next five years. Of the material classes with existing commercial applications, PLA will grow the fastest with a compound annual growth rate of 20.1% for the period 2005-2010. PLA demand is being driven by strong product and applications development by major suppliers such as NatureWorks LLC. Synthetic types will also experience growth approaching 20% per annum over the forecast period. Starch-based polymers are projected to grow at slightly lower rates. This is mainly due to the presence of loose-fill packaging, which is a relatively more mature applications sector. PHA, which started from virtually a zero base in 2005, is projected to grow at close to 60% per annum as commercial scale plants come on stream and better products and processes are introduced.

Demand for biodegradable polymers is being driven by a number of important trends, including:

• Development of supporting framework conditions such as more favourable government regulations to reduce waste packaging and landfill in favour of recycling and composting. Political support is also slowly gaining ground with biodegradable packaging receiving special treatment in some countries such as Germany.

• The world biodegradable plastics industry has agreed a set of standards and certification procedures for biodegradable packaging materials, which will continue to encourage growth and possibly deter imitation.

• Composting infrastructures are being developed by local councils in major towns and cities around the world in response to the problem of packaging waste and over-reliance on landfill in some countries.

• The price differential between biodegradable polymers and petrochemical-based plastics has narrowed during the last two years.

• Growing consumer awareness and preference for sustainable packaging.

• Brand owners are also recognising the benefits of promoting sustainable or ‘green’ packaging.

• There has been a stream of new product and technology development by leading biodegradable polymer suppliers that have opened up new markets and potential applications.

2.2 Material Trends

Product development and improvement has a crucial role to play in the further development of the biodegradable polymers market. These include development of more reliable and lower cost raw materials for manufacture of biodegradable polymers, improvement in performance properties vis- à-vis standard thermoplastics, improvement in processing performance and development of new polymers and blends.

Some of the most interesting material developments covered in the report are as follows.

• New types of renewable feedstock such as palm oil for manufacture of starch-based biodegradable polymers.

• A new generation of PLA materials that can withstand high temperatures and are suitable for microwavable food packaging.

Executive Summary

• New blends of synthetic biopolymers and PLA with better properties and processing performance.

• Plasticiser-free flexible PLA film.

• Development of markets for PLA injection stretch blow moulding applications.

• PLA bottles with higher barrier for oxygen sensitive food and beverages.

• Improvements to biodegradable polymer additive formulations helping to improve processing efficiencies.

• Development of biodegradable polymers with flame retardant properties that can be used for consumer electronics product housing.

• Development of synthetic biodegradable polymers such as polybutylene succinates (PBS) with improved stiffness and thermal properties.

• Progress in fermentation processes and identification of lower cost feedstock for manufacture of PHA products to provide lower material costs.

2.3 Regional Trends

Figure 2.1 shows percentage share of global biodegradable polymer consumption by major world region for 2005.

polymer consumption by major world region for 2005. Figure 2.1 Percentage share of global biodegradable polymer

Figure 2.1 Percentage share of global biodegradable polymer consumption by major world region, 2005

Western Europe is the leading market for biodegradable polymers with 59% of market volumes in 2005. The Western European market has been driven more by regulation than other world regions such as the USA and Japan. These include the European Union directives on packaging waste and landfill which aim to divert a growing amount of packaging waste towards recycling and composting. Europe has also benefited from some of the world’s leading biodegradable producers such as Novamont, Rodenburg Biopolymers and BASF being based in the region.

Biodegradable Polymers

North America has lagged well behind Western Europe in terms of biodegradable polymer market development. Traditionally, there has not been the same degree of urgency to address the issue of waste disposal through landfill in North America because of its enormous landmass. Government and consumer attitudes towards recycling of packaging waste and environmental protection have also militated against market development of sustainable materials.

However, attitudes are slowly changing. During the last few years there have been a number of positive trends that are encouraging biodegradable polymer development including, growth of the composting infrastructure, more institutions looking at food waste diversion from landfill, rising tipping fees for landfill and a better understanding among foodservice suppliers that there is a market for compostable materials.

Japan is the largest consumer of biodegradable polymers in the Asia Pacific region, followed by Australia and New Zealand, with Taiwan, South Korea, Singapore and China, some way behind in terms of market development.

2.4 Market Trends

Biodegradable polymers can be found in a wide range of end use markets although these materials still remain very much niche products. Continued progress in terms of product development and cost reduction will be required before they can effectively compete with conventional plastics for mainstream applications.

Starch-based biodegradable plastics are used for manufacture of various types of bags and sacks, rigid packaging such as thermoformed trays and containers, and loose-fill packaging foam as an alternative to polystyrene and polyethylene. They are also used in agriculture and horticulture for applications such as mulching film, covering film and plant pots. Injection moulding applications include pencil sharpeners, rulers, cartridges, combs and toys.

The main markets for PLA are thermoformed trays and containers for food packaging and food service applications. Other developing areas include films and labels, injection stretch blow moulded bottles and jars, specialty cards and fibres.

Synthetic biodegradable polyesters are used mainly as specialty materials for paper coating, fibres, and garbage bags and sacks. They are also showing up in thermoformed packaging as functional adjuncts to lower-cost biodegradable materials.

Potential applications for PHA include feminine hygiene products, packaging, appliances, electrical and electronics, consumer durables, agriculture and soil stabilisation, nonwovens, biomedical device adhesives, and automotive parts.

Figure 2.2 shows percentage share of global biodegradable polymer consumption by end use market for 2005.

In 2005, packaging (including rigid and flexible packaging, paper coating and foodservice) is the largest sector with 39% of total biodegradable polymer market volumes. Loose-fill packaging is the second largest sector, followed by bags and sacks. Fibres or textiles is an important sector for PLA, and accounts for 9% of total market volumes. Others include a wide range of very small application areas, the most important of which are agriculture and fishing, medical devices, consumer products and hygiene products.

Executive Summary

Executive Summary Figure 2.2 Percentage share of global biodegradable polymer consumption by end use market for

Figure 2.2 Percentage share of global biodegradable polymer consumption by end use market for 2005

2.5 Competitive Trends

There are around thirty suppliers actively involved in the world biodegradable polymers market in 2005. The synthetic biopolymers market is dominated by large, global and vertically integrated chemical companies such as BASF, DuPont, and Mitsubishi Gas Chemicals. The starch and PLA sectors contain mainly specialist biopolymer companies such as Novamont, NatureWorks LLC, Rodenburg Biopolymers and Biotec, which were specifically established purely to develop biodegradable polymers.

The leading suppliers are Novamont, NatureWorks, BASF and Rodenburg Biopolymers, which together represent over 90% of the European market for biodegradable plastics.

Global production capacity for biodegradable polymers has grown dramatically since the mid 1990s. In 1995, production was mainly on a pilot-plant basis with total worldwide capacity amounting to no more than 25-30,000 tonnes. In 2005, global capacity for biodegradable polymers was around 360,000 tonnes. Based on announced projects, total production capacity is set to almost reach 600,000 tonnes by 2008.

At the moment, there are a growing number of biodegradable polymers performing well in niche applications. Many of these materials can be even more cost competitive in the future compared to petroleum-based resins including PET, polyethylene (PE), and polypropylene (PP) as suppliers develop better material properties that can lead to thinner films or lower processing costs.

Historically, pricing had been the biggest barrier to biodegradable polymer market development. However, the competitive position of biodegradable polymers has been improved during the last two years by the sharp upswing in the cost and declining availability of standard petroleum-based resins. Commodity resin prices have climbed steadily since 2003 as oil and natural gas prices have surged. During the period 2003-2005, the average price for competing materials such as polypropylene, general-purpose polystyrene and low density polyethylene (LDPE) have increased between 30-35%. Bottle-grade PET prices have increased by nearly 18%.

At the same time, prices for the three major types of bio-based resins, starch-based biopolymers, polylactic acid (PLA) and aliphatic aromatic co-polyester, have dropped considerably over the last

Biodegradable Polymers

three years as production volumes have increased, more efficient production processes have been deployed and lower cost raw materials have been found.

In 2003, the average price of starch blends was around 3.0-5.0 per kg. In 2005, the average price range of starch blends was down to 1.5-3.5 per kg. PLA is now being sold at prices between 1.37- 2.75 per kg compared to a price range of 3.0-3.5 per kg three years ago, and is now almost price competitive with PET. The average cost of an aliphatic aromatic co-polyester has fallen from 3.5-4.0 per kg in 2003 to 2.75-3.65 per kg in 2005. Prices are expected to fall further for all biodegradable polymer types over time as production volumes increase and unit costs fall.

In terms of the product life cycle, the biodegradable plastics industry has now reached the market introduction stage, having spent the last ten years or so developing their products and processes. The main focus of suppliers was on improving the technology and the products in readiness for full commercialisation. Now, a significant number of products are commercially available and the emphasis has switched to the end user and developing markets and applications.

Brand owners and consumer will have a key role to play in the growth of this industry over the next five to ten years. Buyers are indeed beginning to recognise the marketing value of sustainable materials and are starting to endorse this biopolymers movement. It is education and awareness along with the cost and performance improvements that will take sustainable materials out of niche market status.

While the cost of some biodegradable plastics are high compared with conventional polymers, from a marketing perspective, it is important not only to consider the material cost, but also all associated costs, including the costs of handling and disposal, which are of course lower for biodegradable plastics. Hence, marketing of biodegradable plastics products is most successful when their cost savings and material advantages are exploited to the full. Also, users of biodegradable plastics can differentiate themselves from the competition by demonstrating how innovative and proactive they are for the benefit of the environment.

Applications development to achieve higher production volumes will be crucial for continued market expansion. Production costs for biopolymers still remain high because of low volumes, and profitability of biodegradable plastics products is still too low. Hence, volumes must be increased if unit costs are to fall and profitability is to improve.

3 Overview of Biodegradable Polymers

3.1 Introduction

This chapter begins with an examination of the mechanisms of polymer biodegradation, how biodegradation mechanisms are measured and the factors affecting biodegradation. This is followed by a review of the different classes of biodegradable polymers, their chemical composition, properties, performance characteristics and processing technologies.

3.2 Definitions of Biodegradable Polymers

Biodegradability and compostability are clearly defined by the scientific community and were legally incorporated into a Standard by the American Society for Testing and Materials (ASTM), under reference ASTM D 6400 - 99, in July 1999. Similar definitions have been recognised in several countries around the world, the most significant being DIN CERTCO 54900 in Germany. Harmonisation of the definitions was carried out through the International Biodegradable Products Institute (BPI), which signed a memorandum of understanding with the Japanese Biodegradable Plastics Society and the German DIN CERTCO.

The ASTM defines a biodegradable plastic as a degradable plastic in which the degradation results from the action of naturally occurring microorganisms such as bacteria, fungi and algae.

Composting is defined as a managed process that controls the biological decomposition of biodegradable materials into a humus-like substance called compost; the aerobic and mesophilic and thermophilic degradation of organic matter to make compost; the transformation of biologically decomposable materials through a controlled process of bio-oxidation that proceeds through mesophilic and thermophilic phases and results in the production of carbon dioxide, water, minerals and stabilised organic matter (compost or humus).

Following the international agreement on definitions for biodegradable plastics, specified periods of time, disposal pathways and standard test methodologies were incorporated into the definitions. Standardisation organisations such as CEN, International Standards Organisation (ISO) and American Society for Testing and Materials (ASTM) were consequently encouraged to develop standard biodegradation tests so these could be determined. Society further demanded non-debatable criteria for the evaluation of the suitability of polymeric materials for disposal in specific waste streams such as composting or anaerobic digestion. Biodegradability is usually just one of the essential criteria, besides ecotoxicity and effects on waste treatment processes.

3.3 Mechanisms of Polymer Degradation

Biodegradation is usually defined as degradation caused by biological activity, it will usually occur simultaneously with, and is sometimes initiated by, non-biological degradation such as photodegradation and hydrolysis.

Biodegradable Polymers

Many different polymers are subject to hydrolysis. Different mechanisms of hydrolysis are usually present in most environments. In contrast to enzymic degradation, where a material is degraded gradually from the surface inwards, chemical hydrolysis of a solid material can take place throughout its cross-section, except for very hydrophobic polymers.

Biological degradation takes place through the actions of enzymes or by products (such as acids and peroxides) secreted by microorganisms (bacteria, yeasts, fungi). Also, microorganisms can eat, and sometimes digest polymers, and cause mechanical, chemical and enzymic ageing.

Two steps occur in the microbial polymer degradation process, first, a depolymerisation or chain cleavage step, and second, mineralisation. The first step normally occurs outside the organism due to the size of the polymer chain and the insoluble nature of many of the polymers. Extracellular enzymes are responsible for this step, acting either endo (random cleavage of the internal linkages of the polymer chains) or exo (sequential cleavage of the terminal monomer units in the main chain).

Once sufficiently small size oligomeric or monomeric fragments are formed, they are transported into the cells where they are mineralised. At this stage the cell usually derives metabolic energy from the mineralisation process. The products of this process are gases, water, salts, minerals and biomass. Many variations of this general view of the biodegradation process can occur, depending on the polymer, the organisms and the environment. Nevertheless, there will always be at some stage the involvement of enzymes.

Enzymes are the biological catalysts that can induce massive increases in reaction rates in an environment that is otherwise unfavourable for chemical reactions. All enzymes are proteins with a complex three-dimensional structure ranging in molecular weight from several thousands to several million g/mol. The enzyme activity is closely related to the conformational structure, which creates certain regions at the surface forming an active site. At the active site the interaction between enzyme and substrate takes place, leading to the chemical reaction, eventually giving a particular product. Some enzymes contain regions with absolute specificity for a given substrate while others can recognise a series of substrates. For optimal activity most enzymes must associate with cofactors, which can be of inorganic (such as metal ions) or organic origin (such as coenzymes A, ATP, and vitamins like riboflavin and biotin).

There are an enormous number of different enzymes each catalysing its own unique reaction on groups of substrates or on very specific chemical bonds, in some cases acting complimentarily and in others synergistically. Different enzymes can also have different mechanisms of catalysis. Some enzymes change the substrate through some free radical mechanism while others follow alternative chemical routes (1).

3.4 Measuring Biodegradability of Polymers

Given the various mechanisms available for the biodegradation of a polymer, it will be appreciated that biodegradation does not only depend on the polymer chemistry, but also on the presence of the biological systems involved in the process. When investigating the biodegradability of a material, the effect of the environment cannot be neglected. Microbial activity and hence biodegradability is influenced by the:

• Presence of microorganisms

• Availability of oxygen

Overview of Biodegradable Polymers

• Amount of available water

• Temperature

• Chemical environment (pH, electrolytes etc.)

In order to simplify the overall picture, the environments in which biodegradation occurs are divided into two environments, aerobic, where oxygen is available, and anaerobic, where no oxygen is present. These two can in turn be subdivided into aquatic and high solids environments.

The high solids environment is the most relevant for measuring the biodegradation of polymeric materials, since they represent the conditions during biological municipal solid waste treatment such as composting. However, possible applications of biodegradable materials other than in packaging and consumer products (such as fishing nets at sea) explain the necessity of aquatic biodegradation tests.

Numerous methods to measure the biodegradability of polymers have been developed. Because of slightly different definitions or interpretation of the term ‘biodegradability’, the different approaches are therefore not equivalent in terms of information they provide or the practical significance. Since the typical exposure environment involves incubation of a polymer substrate with microorganisms or enzymes, only a limited number of measurements are possible. These include those pertaining to the substrates, to the microorganisms, or to the reactive products.

Four common approaches available for studying biodegradation processes are used.

• Monitoring microbial growth

• Monitoring the depletion of substrates

• Monitoring reaction products

• Monitoring changes in substrate properties

Measurements for testing the biodegradability of polymers are usually based on one or more of these four basic approaches (2).

3.5 Factors Affecting Biodegradability

The environment is an important factor affecting the rate and degree of biodegradation of polymer substrates. The other key aspects determining biodegradability are related to the chemical composition of the polymer. The polymer chemistry governs the chemical and physical properties of the material and its interaction with the physical environment, which in turn affects the material’s compostability with particular degradation mechanisms.

Many attempts have been made to correlate polymer structure to biodegradability. However, this proved to be challenging and so far only few general relationships between structure and biodegradability have been formulated. In many cases complex interplay between some of the different factors occur simultaneously, often causing difficulty in sorting out primary effects and correlations. Some of the general factors affecting biodegradability are listed below, but it should be considered that many exceptions to the norm have also been reported.

The accessibility of the polymer to water-borne enzymes is vitally important because the first step in the degradation of plastics usually involves the actions of extracellular enzymes, which break down

Biodegradable Polymers

the polymer into products small enough to be assimilated. Therefore, the physical state of the plastic and the surface offered for attack, are important factors. Biodegradability is usually also affected by the hydrophilic nature (wettability) and the crystallinity of the polymer. A semi-crystalline nature tends to limit the accessibility, essentially confining the degradation to the amorphous region of the polymer. However, contradictory results have been reported. For example, highly crystalline starch materials and bacterial polyesters, are rapidly hydrolysed.

The chemical properties that are important include the:

• Chemical linkage in the polymer backbone.

• Pendant groups, their position and their chemical activity.

• End-groups and their chemical activity.

Linkage involving hetero atoms, such as ester and amide bonds, are considered susceptible to enzymic degradation. However, this is not the case for polyamides, aromatic polyesters and many other polymers containing hetero atoms in the main chain. The stereo-chemistry of the monomer units along the polymer chain also influences biodegradation rates, since an inherent property of many enzymes is their stereo-chemical selectivity. The stereo-chemistry may nevertheless not be observed when a broad spectrum of microorganisms are used instead of enzyme solutions with high stereo-specificity.

The molecular weight distribution of the polymer can have a dramatic effect on rates of depolymerisation. This effect has been demonstrated for a number of polymers, where a critical lower limit must be present before the process will start. The molecular origin for this effect is still subject to speculation, and has been attributed to a range of causes such as changes in enzyme accessibility, chain flexibility, fits with active sites, crystallinity or other aspects of morphology.

Interaction with other polymers (blends) also affects the biodegradation properties. These additional materials may act as barriers to prevent migration of microorganisms, enzymes, moisture or oxygen into the polymer domain of interest. The susceptibility of a biodegradable polymer to microbial attack is sometimes decreased by grafting it onto a non-biodegradable polymer, or by crosslinking. On the other hand, it has sometimes been suggested that combining a non-biodegradable polymer with one that is biodegradable, or grafting a biodegradable polymer onto a non-biodegradable backbone polymer may result in a biodegradable system. Whether the non-biodegradable component is in fact mineralised, however, is usually disregarded (3).

3.6 Biodegradable Polymer Classes

There are broadly three classes of commercially available biodegradable polymers in existence.

1. Unmodified polymers that are naturally susceptible to microbial-enzyme attack.

2. Synthetic polymers, primarily polyesters.

3. Naturally biodegradable polymers that have been modified with additives and fillers.

Naturally biodegradable polymers produced in nature are renewable. Some synthetic polymers are also renewable because they are made from renewable feedstock, for example polylactic acid is derived from agricultural feedstock.

Overview of Biodegradable Polymers

3.6.1 Naturally Biodegradable Polymers

Natural polymers are produced in nature by all living organisms. Biodegradation reactions are typically enzyme-catalysed and occur in aqueous media. Natural macromolecules containing hydrolysable linkages, such as protein, cellulose, and starch, are generally susceptible to biodegradation by the hydrolytic enzymes of microorganisms. Thus the hydrophilic/hydrophobic character of polymers greatly affects their biodegradability. It also has a great impact on their performance and durability in humid conditions.

Polysacharides such as starch are the most prevalent naturally biodegradable polymer in commercial use. Aliphatic polyesters such as polyhydroxyalkanoates (PHA) are also a family of easily biodegradable polymers found in nature that are beginning to find commercial use.

3.6.2 Synthetic Biodegradable Polymers

While natural polymers are produced by living organisms, synthetic biodegradable polymers are only produced by mankind. Biodegradation reactions are the same for both, i.e., typically enzyme-catalysed and produced in aqueous media. The major category of synthetic biodegradable polymers consists of aliphatic polyesters with a hydrolysable linkage along the polymer chain such as polylactic acid (PLA). Other widely available synthetic types include aliphatic/aromatic co-polyesters.

3.6.3 Modified Naturally Biodegradable Polymers

Over the last thirty years or so, many attempts have been made to improve the biodegradability of synthetic polymers by incorporating polysaccharide-derived materials. The most prominent modified naturally biodegradable polymer in commercial use is produced by Novamont under the Mater-Bi trade name. This starch-based technology is unique because the modification goes beyond conventional compounding. The starch is destructurised by applying sufficient work and heat to almost completely destroy the crystallinity of amylose and amylopectine in the presence of macromolecules able to form a complex with amylose. Novamont produces several different classes of Mater-Bi, all containing starch with different classes of synthetic components such as polycaprolactone (PCL). The material obtained is suitable for producing film and sheet, foams and injection moulding.

For the purpose of this report, four classes of commercially available biodegradable polymers are examined.

1. Starch based biodegradable polymers (including modified starch blends)

2. Polyhydroxyalkanoates (PHA)

3. Polylactic acid (PLA)

4. Synthetic biodegradable polymers such as aliphatic-aromatic co-polyesters.

The following sections discuss the chemical composition, properties and production of each biodegradable polymer type in more detail.

Biodegradable Polymers

3.7 Starch-Based Biodegradable Polymers

In nature, the availability of starch is just second to cellulose. The most important industrial sources of starch are corn, wheat, potato, tapioca and rice. In the last decade, there has been a significant reduction in the price of corn and potato starch, both in Europe and the USA. The lower price and greater availability of starch associated with its very favourable environmental profile aroused a renewed interest in development of starch-based polymers as an alternative to polymers based on petrochemicals.

Starch is totally biodegradable in a variety of environments and thus permits the development of totally degradable products for specific market demands. Degradation or incineration of starch- based products recycles atmospheric carbon dioxides trapped by starch-producing plants and does not increase potential global warming.

The most relevant achievements in this sector are related to thermoplastic starch polymers resulting from the processing of native starch by chemical, thermal and mechanical means, and to its complexation to other co-polymers. The resulting materials show properties ranging from the flexibility of polyethylene to the rigidity of polystyrene, and can be soluble or insoluble in water as well as insensitive to humidity. Such properties explain the leading position of starch-based materials in the biodegradable polymer field.

Starch is unique among carbohydrates because it occurs naturally as discrete granules. This is because the short-branched amylopectin chains are able to form helical structures, which crystallise. Starch granules exhibit hydrophilic properties and strong intermolecular association via hydrogen bonding due to the hydroxyl groups on the granule surface. The melting point of native starch is higher than the thermal decomposition temperature: hence the poor thermal stability of native starch and the need for conversion to starch-based materials with a much-improved property profile.

In nature, starch is based on crystalline beads of about 15-100 microns in diameter. Crystalline starch beads in plastics can be used as fillers or can be transformed into thermoplastic starch, which can either be processed alone or in combination with specific synthetic polymers. To make starch thermoplastic, its crystalline structure has to be destroyed by pressure, heat, mechanical work or use of plasticisers. Three main families of starch polymer can be used: pure starch, modified starch and fermented starch polymers.

The production of starch polymers begins with the extraction of starch. Taking as an example corn; starch is extracted from the kernel by wet milling. The kernel is first softened by steeping it in a dilute acid solution, then ground coarsely to split the kernel and remove the oil-containing germ. The starch slurry is then washed in a centrifuge, dewatered and dried. Either prior, or subsequent to the drying step, the starch may be processed in a number of ways to improve its properties.

The addition of chemicals leading to alteration of the structure of starch is generally described as ‘chemical modification’. Modified starch is starch that has been treated with chemicals so that some hydroxyl groups have been replaced by for example ester or ether groups. High starch content plastics are highly hydrophilic and readily disintegrate when in contact with water. Very low levels of chemical modification can significantly improve hydrophilicity, as well as change other rheological, physical and chemical properties of starch.

Crosslinking, in which two hydroxyl groups or neighbouring starch molecules are linked chemically is also a form of chemical modification. Crosslinking inhibits granule swelling or gelatinisation and gives increased stability to acid, heat treatment and shear forces. Chemically modified starch may be used directly or palletised or otherwise dried for conversion to a final product.

Overview of Biodegradable Polymers

Starch can also be modified by fermentation as used in the Rodenburg process. In this case the raw material is a potato waste slurry originating from the food industry. The slurry mainly consists of starch, the rest being proteins, fats and oils, inorganic components and cellulose. The slurry is held in storage silos for about two weeks to allow for stabilisation and partial fermentation. The most important fermentation process that occurs is the conversion of a small fraction of starch to lactic acid by mans of the lactic acid bacteria that are naturally present in the feedstock. The product is subsequently dried to a final water content of 10% and then extruded.

Starch-based polymers have been the most studied class of biodegradable polymer for their extrusion characteristics. Extrusion processing plays a large role in establishing the polymer properties. Starch can be made thermoplastic by using technology very similar to extrusion cooking. Starch exists as granular beads of about 15-100 microns in diameter that can be compounded with another synthetic polymer as a filler. However, under special heat and shear conditions during extrusion it can be transformed into an amorphous thermoplastic by a process known as destructurising.

Starch can be destructured in the presence of more hydrophobic polymers such as aliphatic polyesters. Aliphatic polyesters with low melting points are difficult to process by conventional techniques such as film blowing and blow moulding. Films such as polycaprolactones (PCL) are tacky as extruded and have a low melt strength (over 130 °C). Also, the slow crystallisation of the polymer causes the properties to change with time. Blending starch with aliphatic polyesters improves processability and biodegradability.

Addition of starch has a nucleating effect, which increases the rate of crystallisation. The rheology of starch/PCL blends depends on the extent of starch granule destruction and the formation of thermoplastic starch during extrusion. Increasing the heat and shear intensities can reduce the melt viscosity, but enhance the extrudate-swell properties of the polymer.

Starch/aliphatic polyester compositions are prepared by blending a starch-based component and an aliphatic polyester in a co-rotating, intermeshing twin-screw extruder. The co-rotating, self-cleaning screw on these machines prevents caking and churning of cooked starch. Temperature and pressure conditions are such that the starch is destructurised and the composition forms a thermoplastic melt. The resulting material has an interpenetrated or partially interpenetrated structure.

Novamont is easily market leader for starch-based biodegradable plastics. Under the Mater-Bi trade name, Novamont offers a wide range of materials divided into five product families by processing technology. These are film, extrusion/thermoforming, injection moulding, foaming and tyre technology. Mater-Bi products are mainly used in specific applications where biodegradability is required. Examples include composting bags and sacks, foodservice products such as single serve cups, containers and plates, foam for industrial packaging, film wrapping, laminated paper, agricultural film products, slow release devices and hygiene products.

Mater-Bi is characterised by the following properties.

• Use performance similar to traditional plastics

• Processing performance similar or better than traditional plastics

• Wide range of mechanical properties from soft and tough material to rigid

• Antistatic behaviour

• Compostability in a wide range of composting conditions

Biodegradable Polymers

Other leading starch-based biodegradable polymer manufacturers are Biotec and BIOP Biopolymers.

Following the sale of the film business to Novamont in 2000, Biotec offers starch-based materials for foodservice products and pharmaceutical applications.

BIOP Biopolymer Technologies offers a starch-based material comprising an additive consisting of a vinyl alcohol/vinyl acetate copolymer, sold under the Biopar trade name (4).

3.8 Polyhydroxyalkanoates

Polyhydroxyalkonates (PHA) is a term given to a family of aliphatic polyesters produced by microorganisms that are fully biodegradable. They offer a wide array of physical properties that can range from stiff and brittle plastics to elastomers.

An attractive feature of PHAs is the ability to produce them using renewable carbon resources. PHA can be produced using renewable carbon sources such as sugars and plant oils. Various waste materials are also being considered for potential carbon sources for PHA production, including whey, molasses and starch. The carbon source available to a microorganism is one of the factors (others being the PHA synthase substrate specificity and the types of biochemical pathways available) that determine the type of PHA produced. For industrial scale production, the carbon source significantly contributes to the final cost. This makes the carbon source one of the most important components in the production of PHA and is therefore a prime target for potential cost reduction.

PHAs are mainly composed of R-(-)-3-hydroxyalkanoic acid monomers. These can be broadly subdivided into two groups:

Short chain length PHAs

• consist of 3 carbon - 5 carbon monomers (C3-C5)

• produced by bacterium Alcaligenes eutrophus (plus others)

Long chain length PHAs

• consist of 6 carbon - 14 carbon monomers (C6-C14)

• produced by Pseudomonas oleovorans (plus others)

Each type of PHA generally consists of 1000-10000 monomers, but most are synthesised by short chain length monomers.

There are many different types of PHA, distinctly characterised by chain length, type of functional group and degree of unsaturated bonds. A higher degree of unsaturation increases the rubber qualities of a polymer, and different functional groups change the physical and chemical properties of a polymer.

PHB (or poly-3-hydroxybutyrate (P(3HB))) is the most common type of PHA produced and is an example of a short chain length homopolymer produced by A. eutrophus. PHB has poor physical properties for commercial use, as it is stiff, brittle and hard to process. This has led to an increased interest to produce heteropolymers with improved qualities.

Overview of Biodegradable Polymers

Biopol, produced by Metabolix, is a leading example of an improved poly(3-hydroxybutyrate-co- 3-hydroxyvalerate), P(3HB-3HV), heteropolymer. Compared to PHB, P(3HB-3HV) is less stiff, tougher, and easier to process, making it more suitable for commercial production. It is also water resistant and impermeable to oxygen, increasing its value.

PHB is a completely biodegradable polymer and degrades through various types of bacteria and fungi to carbon dioxide and water through secreting enzymes. It can also be degraded through non- enzymatic hydrolysis. Degradation appears to be the fastest under conditions of high temperatures and mechanical disruption. PHB is also biocompatible, meaning it is a metabolite normally present in blood.

The production of biodegradable polymers using carbon as the starting material can be carried out using a 3-stage or a 2-stage process.

The 3-stage process involves utilisation of plant sugars derived from photosynthetically fixed CO 2 as carbon sources in the fermentation of organic acids, alcohols and amino acids. These substances are then used as building blocks for the chemical synthesis of polymers. Examples of polymers using the 3-stage process include polylactic acid and polybutylene succinate.

On the other hand, the 2-stage process involves the direct conversion of plant sugars and plant oils into polymer by microorganisms. At present, the biosynthesis of PHA is largely carried out through the 2-stage process. Compared to the 3-stage process of polymer production, the 2-stage process can be more cost effective provided that excellent producers of PHA are identified and the fermentation process is highly optimised. Inexpensive plant oils have been found to be an excellent carbon source for the efficient production of PHA.

There were a number of efforts to commercialise PHA, notably by ICI in the 1980s and early 1990s, and by Monsanto in the mid 1990s. However, these attempts were largely unsuccessful due to the high cost and very limited processability and properties. In recent years, these deficiencies have been largely overcome most notably by Metabolix and by Procter & Gamble’s Nodax business unit, which both specialise in PHA materials development.

The broad range of properties offered by PHA make them useful for a wide variety of applications, including:

Food packaging

Single-serve cups and other disposable foodservice items

Houseware

Appliances

Electrical and electronics

Consumer durables

Agriculture and soil stabilisation

Adhesives, paints and coatings

Automotive

Medical (bone plates and surgical sutures)

Biodegradable Polymers

3.9 Polylactic Acid Polyesters

Polylactic acid (PLA) is a biodegradable polymer derived from lactic acid. It is a highly versatile material and is made from 100% renewable resources like corn, sugar beet, wheat and other starch- rich products. Polylactic acid exhibits many properties that are equivalent to or better than many petroleum-based plastics, which makes it suitable for a variety of applications.

The starting material for polylactic acid is starch from a renewable resource such as corn. Corn is milled, which separates starch from the raw material. Unrefined dextrose is then processed from the starch. Dextrose is turned into lactic acid using fermentation, similar to that used by beer and wine producers.

Polylactide (PLA) polymer chemistry stems from lactide, which is the cyclic dimer of lactic acid that exists as two optical isomers, d and l. l-lactide is the naturally occurring isomer, and dl-lactide is the synthetic blend of d-lactide and l-lactide. The homopolymer of l-lactide (LPLA) is a semicrystalline polymer. Poly(dl-lactide) (DLPLA) is an amorphous polymer exhibiting a random distribution of both isomeric forms of lactic acid, and accordingly is unable to arrange into an organised crystalline structure. This material has lower tensile strength, higher elongation, and a much more rapid degradation time. PLA is about 37% crystalline, with a melting point of 175-178 °C and a glass-transition temperature of 60-65 °C. The degradation time of LPLA is much slower than that of DLPLA, requiring more than two years to be completely absorbed. Copolymers of l-lactide and dl-lactide have been developed prepared to disrupt the crystallinity of l-lactide and accelerate the degradation process.

Turning the lactic acid into a polymer involves a chemical process called condensation, whereby two lactic acid molecules are converted into one cyclic molecule called a lactide. This lactide is purified through vacuum distillation. A solvent-free melt process causes the ring-shaped lactide polymers to open and join end-to-end to form long chain polymers. A wide range of products that vary in molecular weight and crystallinity can be produced, allowing the PLA to be modified for a variety of applications.

PLA compares well with petrochemical-based plastics used for packaging. It is clear and naturally glossy like polystyrene, it is resistant to moisture and grease, it has flavour and odour barrier characteristics similar to polyethylene terephthalate (PET). The tensile strength and modulus of elasticity of PLA is also comparable to PET.

PLA can be formulated to be either rigid or flexible and can be co-polymerised with other materials. Polylactic acid can be made with different mechanical properties suitable for specific manufacturing processes, such as injection moulding, sheet extrusion, blow moulding, thermoforming, film forming and fibre spinning using most conventional techniques and equipment.

PLA is a non-volatile, odourless polymer and is classified as GRAS (generally recognised as safe) by the US Food and Drug Administration.

Polylactic acid has been around for many decades. In 1932, Wallace Carothers, a scientist for DuPont, produced a low molecular weight product by heating lactic acid under a vacuum. In 1954, after further refinements, DuPont patented Carothers’ process.

Due to high costs, the focus was initially on the manufacture of medical grade sutures, implants and controlled drug release applications. Recently, there have been advances in fermentation of glucose, which turns the glucose into lactic acid. This has dramatically lowered the cost of producing lactic acid and significantly increased interest in the polymer.

Overview of Biodegradable Polymers

Cargill, Incorporated, was one of the first companies to extensively develop polylactic acid polymers. Cargill began researching PLA production technology in 1987. It began production of pilot plant quantities in 1992 and in 1997 formed a joint venture with Dow Chemical Company, Inc., creating Cargill Dow Polymers LLC. The joint venture is dedicated to further commercialising PLA polymers and formally launched NatureWorks TM PLA technology in 2001. Construction was completed on a large-scale PLA manufacturing facility in Blair, Nebraska in 2002. Cargill Dow now trades as NatureWorks LLC, following the sale by Dow Chemicals of its share in the joint venture to Cargill Inc. in 2005.

Polylactic acid has many potential uses, including many applications in the textile and medical industries as well as the packaging industry.

The main types of NatureWorks PLA that are available for packaging applications include general purpose film grades, extrusion coating, extrusion and thermoforming grades and injection stretch blow moulding.

The general purpose film grade is ‘biaxially oriented’, a property that gives it stability at temperatures up to 130 °C. They also offer a biaxially oriented film for high temperature applications (150 °C). According to NatureWorks, these resins offer excellent optical properties, good machinability and excellent twist and dead fold characteristics. These polymers are offered in common pellet form, which should allow for rapid adoption with conventional extruders.

Grades designed for extrusion coating on paper, process easily on conventional extrusion coating equipment at a lower melt extrusion temperature than polyethylene coatings according to the company. Paper and board coated in this resin can be heat-sealed on typical equipment. Potential applications for these grades include, lawn and leaf bags, hot and cold drinking cups, picnic plates, bowls, straws, fried food boxes, frozen vegetable packaging, and liquid food packaging.

Clear extrusion sheet grades are designed for extrusion and thermoforming applications, and like other NatureWorks’ PLA polymers, use conventional processing techniques and equipment. Potential uses include dairy containers, food service ware, transparent food containers, blister packs, and cold drink cups.

PLA is available in grades suitable for manufacture of injection stretch blow moulded bottles. It is claimed these offer comparable organoleptic properties to glass and PET making it suitable for a variety of short shelf-life food and beverage bottling applications.

NatureWorks LLC is also developing grades for microwavable packaging and bottles for packaging oxygen sensitive food and beverages using barrier-enhanced PLA.

Polylactic acid also has many potential uses in fibres and non-wovens. It is easily converted into a variety of fibre forms using conventional melt-spinning processes. Spunbound and meltblown non- wovens as well as monocomponent, bicomponent, continuous (flat and textured) and stable fibres are all easily produced.

Polylactic acid based fibres have various attributes that make them attractive for many traditional applications. PLA polymers are more hydrophilic than PET, have a lower density, and have excellent crimp and crimp retention. Shrinkage of PLA materials and thermal bonding temperatures are easily controllable. These polymers tend to be stable to ultraviolet light resulting in fabrics that show little fading. They also offer low flammability and smoke generation characteristics.

Biodegradable Polymers

Major applications for PLA fibres and non-wovens include clothing and furnishings such as drapes, upholstery and covers. Some interesting potential applications include household and industrial wipes, diapers, feminine hygiene products, disposable garments, and UV resistant fabrics for exterior use (awnings, ground covers).

In the field of biomedical devices, polylactic acid has become an important material, having been in use for over 25 years. Polylactic acid is a biodegradable, bioresorbable polymer, i.e., it can be assimilated by a biological system. Since PLA can be assimilated by the body, it has found applications in sustained release drug delivery systems. Furthermore, its mechanical properties and absorbability make PLA polymer an ideal candidate for implants in bone or soft tissue (facial traumatology, orthopaedic surgery, ophthalmology, orthodontics, local implants for controlled release of anti-cancer drugs), and for resorbable sutures (eye surgery, conjunctional surgery, surgery of the chest and abdomen).

The mechanical, pharmaceutical and bioabsorption characteristics are dependent on controllable parameters such as chemical composition and molecular weight of the polymer. The time frame for resorption of the polymer may be anything from just a few weeks to a few years, and can be regulated by use of different formulations and the addition of radicals on its chains.

PLA polymers are fully compostable in commercial composting facilities. With proper equipment, PLA can be converted back to monomer, which then can be converted back into polymers. Alternatively, PLA can be biodegraded into water, carbon dioxide and organic material. At the end of a PLA-based product’s life cycle, a product made from PLA can be broken down into its simplest parts so that no sign of the original product remains.

3.10 Synthetic Biodegradable Polymers

Polyesters have played a prominent part in the development of biodegradable polymers. One of the first products developed as a biodegradable plastic in the early 1970s was based on a polyester belonging to the polyhydroxyalknoates (PHA) group, called polyhydroxybutyrate (PHB).

Beside the natural polyesters a number of synthetic aliphatic polyesters have also been shown to be biodegradable. From a commercial point of view the most important synthetic biodegradable aliphatic polyester was traditionally polycaprolactone (PCL).

3.10.1 Polycaprolactone (PCL)

The ring-opening polymerisation of ε-caprolactone yields a semicrystalline polymer with a melting point of 59-64 °C and a glass transition temperature of -60 °C. The polymer is regarded as tissue compatible and was originally used in the medical field as a biodegradable suture in Europe. Because the homopolymer has a degradation time of the order of two years, copolymers have been synthesised to accelerate the rate of bioabsorption. For example, copolymers of ε-caprolactone with dl-lactide have yielded materials with more rapid degradation rates.

Polycaprolactone aliphatic polyesters have long been available from companies such as Solvay and Union Carbide (now Dow Performance Chemicals) for use in adhesives, compatibilisers, modifiers and films as well as medical applications. These materials have low melting points and high prices

( 4-7 per kg in 2005). PCL is predominantly used as a component in polyester/starch blends such as

Overview of Biodegradable Polymers

Mater-Bi as produced by Novamont. Caprolactone limits moisture sensitivity, boosts melt strength, and helps plasticise the starch.

Other types of synthetic biopolymers that have been in use for medical applications for a number of years are polyglycolide, polydioxanone and poly(lactide-co-glycolide).

3.10.2 Polyglycolide (PGA)

Polyglycolide is the simplest linear aliphatic polyester. PGA was used to develop the first totally synthetic absorbable suture, marketed as Dexon in the 1960s by Davis and Geck, Inc. Glycolide monomer is synthesised from the dimerisation of glycolic acid. Ring-opening polymerisation yields high molecular-weight materials, with approximately 1-3% residual monomer present. PGA is highly crystalline (45-55%), with a high melting point (220-225 °C) and a glass transition temperature of 35-40 °C. Because of its high degree of crystallisation, it is not soluble in most organic solvents; the exceptions are highly fluorinated organics such as hexafluoroisopropanol. PGA fibres 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 to 6 months. Glycolide has been copolymerised with other monomers to reduce the stiffness of the resulting fibers.

3.10.3 Poly(dioxanone) (a polyether-ester)

The ring-opening polymerisation of p-dioxanone resulted in the first clinically tested monofilament synthetic suture, known as PDS (marketed by Ethicon). This material has approximately 55% crystallinity, with a glass-transition temperature of -10 to 0 °C. The polymer should be processed at the lowest possible temperature to prevent depolymerisation back to monomer. Poly(dioxanone) has demonstrated no acute or toxic effects on implantation. The monofilament loses 50% of its initial breaking strength after three weeks and is absorbed within six months, providing an advantage over other products for slow-healing wounds.

3.10.4 Poly(lactide-co-glycolide)

Using the polyglycolide and poly(l-lactide) properties as a starting point, it is possible to co-polymerise the two monomers to extend the range of homopolymer properties. Copolymers of glycolide with both l-lactide and dl-lactide have been developed for both device and drug delivery applications. It is important to note that there is not a linear relationship between the copolymer composition and the mechanical and degradation properties of the materials. For example, a copolymer of 50% glycolide and 50% dl-lactide degrades faster than either homopolymer. Copolymers of l-lactide with 25-70% glycolide are amorphous due to the disruption of the regularity of the polymer chain by the other monomer. A copolymer of 90% glycolide and 10% l-lactide was developed by Ethicon as an absorbable suture material under the trade name Vicryl. It absorbs within 3 to 4 months but has a slightly longer strength retention time.

Nowadays, various aliphatic copolyesters based on succinate, adipate, ethylene glycol and 1,4- butanediol are being produced. Aliphatic polyesters based on natural feedstock such lactic acid are also being produced on a commercial scale by companies such as NatureWorks LLC.

Biodegradable Polymers

However, most of the aliphatic polyesters presently commercially used for biodegradable materials exhibit serious disadvantages. Beside the relatively high price level, properties are often limited and exclude these materials from many applications. For example, PCL has a very low melting point of about 60 ºC.

For conventional technical applications aromatic polyesters such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT) are widely used. But these polymers are biologically inert and thus not directly applicable as biodegradable plastics. Combining both the excellent material properties of aromatic polyesters and the potential biodegradability of aliphatic polyesters has led to the development of a number of commercially available aliphatic-aromatic co-polyesters over the last decade or so.

BASF’s Ecoflex is based on a co-polyester from terephthalic acid, adipic acid and 1,4-butanediol. The content of terephthalic acid in the polymer is approximately 42-45 mol% (with regard to the dicarboxylic monomers). Modification of the basic co-polyester lead to a flexible material, which is especially suitable for film applications.

Ecoflex reportedly processes easily and has a melting point of 110-115 °C and other properties equal or close to those of LDPE. The F (film) version imparts high elongation and dart impact and yields clear films that weld and print easily, BASF says. masterbatches can fine-tune the feel of Ecoflex films from soft to HDPE-like stiffness. Ecoflex is said to have high toughness and good cling properties. That makes it possible for 10 micron cling films to replace vinyl in vegetable, fruit, and meat wraps. BASF claims its materials also make films with 50% lower moisture vapour transmission rate (MVTR) than other biodegradable polymers.

The biodegradation of Ecoflex film was tested under composting conditions. After 100 days in a composting environment more than 90% of the carbon in the polymer was converted to carbon dioxide. Tests also showed no toxic effects of degradation intermediates.

Eastar Bio (now owned by Novamont) is also based on a co-polyester composed of terephthalic acid, adipic acid and 1,4-butanediol, but due to some special modifications the material properties are different.

Degradation of Eastar Bio was tested under composting conditions: after 210 days of composting about 80% of the polymer carbon was released as carbon dioxide.

Eastar Bio co-polyesters have a melting point of 108 °C and offer good contact clarity, adhesion, and elongation (up to 800%). They have high moisture and grease resistance, and process much like LDPE. Eastar Bio is used in lawn-and-garden bags, agricultural films, netting, and paper coatings.

DuPont’s Biomax product is a standard PET with the addition of three aliphatic monomers to allow degradation to take place. Comparable to PLA, the degradation mechanism is described as an initial attack of water to the special monomers, which are sensitive to hydrolysis. Although it appears that Biomax sufficiently disintegrates under composting conditions, the process of decomposition of the material was too slow to meet accepted standards.

Biomax 6962 has 1.35 g/cc density and 195 °C melting point versus 250 °C for PET, resulting in higher service temperature capability and faster processing rates than for other biodegradables. Mechanical properties include high stiffness and 40% to 50% elongation. DuPont has targeted fast- food disposable packaging, as well as yard-waste bags, diaper backing, agricultural film, flowerpots and bottles.

Overview of Biodegradable Polymers

EnPol from Korea’s IRe Chemicals are based on a group of aliphatic co-polyesters comprising adipic acid, succinic acid, 1,2-ethanediol or 1,4-butanediol. EnPol polymers meet the specifications of the US Food & Drug Administration for food contact applications and the USP specifications for medical device applications.

The biodegradation of EnPol polymers was tested in a controlled laboratory composting test and showed that within 45 days a carbon dioxide evolution of more than 90% of the carbon present in the co-polyester was detected.

Partly because of their cost, biodegradable polyesters are finding much of their market in blends. Synthetic biodegradable polyesters tend to complement one another’s properties, as well as those of PLA, thermoplastic starch, and other organic materials. Eastar Bio, for instance, is flexible and tough, with good contact clarity and adhesion properties. Its deficits are relatively low stiffness, poor melt strength, and a tendency to stick in injection moulds. In contrast, NatureWorks PLA tends to be brittle and has poor adhesion. Blends of the two are a logical way to increase the performance envelope of both materials.

3.11 Processing Biodegradable Polymers

3.11.1 Introduction

All commercially available biodegradable polymers can be melt processed by conventional means such as injection moulding, compression moulding, and extrusion. Special consideration needs to be given to the exclusion of moisture from the material before melt processing to prevent hydrolytic degradation. Care must be taken to dry the polymers before processing and to rigorously exclude humidity during processing.

Because most biodegradable polymers have been synthesised by ring-opening polymerisation, a thermodynamic equilibrium exists between the forward or polymerisation reaction and the reverse reaction that results in monomer formation. Excessively high processing temperatures may result in monomer formation during the moulding or extrusion process. The presence of excess monomer can act as a plasticiser, changing the material’s mechanical properties, and can catalyze the hydrolysis of the device, thus altering degradation kinetics. Therefore, these materials should be processed at the lowest temperatures possible.

3.11.2 Film Blowing and Casting

There are two main processes used commercially for making film from thermoplastics, blowing and casting.

Blown film is one of the most common methods of film manufacture (also referred to as tubular film extrusion). The process involves extrusion of a plastic through a circular die, followed by ‘bubble-like’ expansion. The principal advantages of manufacturing film by this process include the ability to:

• produce tubing (both flat and gussetted) in a single operation

• regulation of film width and thickness by control of the volume of air in the bubble, the output of the extruder and the speed of the haul-off

Biodegradable Polymers

• eliminate end effects such as edge bead trim and non uniform temperature that can result from flat die film extrusion

• capability of biaxial orientation (allowing uniformity of mechanical properties)

The production process for blown film begins with plastic melt being extruded through an annular slit die, usually vertically, to form a thin walled tube. Air is introduced via a hole in the centre of the die to blow up the tube like a balloon. Mounted on top of the die, a high-speed air ring blows onto the hot film to cool it. The tube of film then continues upwards, continually cooling, until it passes through nip rolls where the tube is flattened to create what is known as a ‘lay-flat’ tube of film. This lay-flat or collapsed tube is then taken back down the extrusion ‘tower’ via more rollers. On higher output lines, the air inside the bubble is also exchanged. This is known as internal bubble cooling.

The lay-flat film is then either kept as such or the edges of the lay-flat are slit off to produce two flat film sheets and wound up onto reels. If kept as lay-flat, the tube of film is made into bags by sealing across the width of film and cutting or perforating to make each bag. This is done either in line with the blown film process or at a later stage.

Typically, the expansion ratio between die and blown tube of film would be 1.5 to 4 times the die diameter. The drawdown between the melt wall thickness and the cooled film thickness occurs in both radial and longitudinal directions and is easily controlled by changing the volume of air inside the bubble and by altering the haul off speed. This gives blown film a better balance of properties than traditional cast or extruded film, which is drawn down along the extrusion direction only.

Polyethylenes (HDPE, LDPE and LLDPE) are the most common resins in use, but a wide variety of other materials can be used as blends with these resins or as single layers in a multi-layer film structure. Blown film can be used either in tube form (e.g., for plastic bags and sacks) or the tube can be slit to form a sheet. Typical applications include packaging (e.g., shrink film, stretch film, bag film or container liners), consumer packaging (e.g., packaging film for frozen products, shrink film for transport packaging, food wrap film, packaging bags, or form-fill-and-seal packaging film).

The process for making a cast film involves drawing a molten web of resin from a die onto a roll for controlled cooling. The cast film process is used to make a film with gloss and sparkle. The melt temperature in the cast film process is higher than in the blown film process. The higher the melt temperature the better are the optical properties of the film.

Most biodegradable polymers are suitable for film blowing and casting, although modifications are often necessary, and productivity may not be as high as conventional thermoplastics. For example, starch-based Mater-Bi films can be produced by film blowing and casting equipment traditionally used for LDPE with little or no modification. Film production productivity is reported to be 80-90% of LDPE. The main difference from traditional PE film is the lower welding temperatures, therefore small to medium sized production lines with good cooling capacity are the best suited for processing starch-based film.

PLA films with thicknesses of 8-510 microns have been obtained from commercial film casting equipment. PLA can be difficult to process into a film due to instability at elevated processing temperatures. According to NatureWorks, melt stable PLA suitable for processing into film can be made by controlling the polymer composition as well as adding stabilising or catalyst-destabilising agents. The polymer molecular weight (MW) plays a role in its processability. Also, polymer morphology is very important. Semi-crystalline PLA is suitable for processing into films with desirable barrier properties. The desired range of compositions for semi-crystalline PLA is less than 15 wt% meso-lactide, and the remaining weight percent being L-lactide.

Overview of Biodegradable Polymers

Crystallisation of a thermoplastic must occur within a few seconds for efficient film processing. NatureWorks has patented four methods to increase the rate of PLA crystallisation:

1. Adding a plasticising agent such as dioctyl adipate.

2. Adding a nucleating agent such as talc.

3. Orientation by drawing during film casting or blowing or after it has cast or blown.

4. Heat setting, which involves holding constrained oriented film at temperatures above the glass transition temperature (Tg).

3.11.3 Injection Moulding

Injection moulding is one of the prime processes for producing plastics articles. It is a fast process and is used to produce large numbers of identical items from high precision engineering components to disposable consumer goods. Most thermoplastics can be processed using injection moulding. Some of the most commonly used include ABS, nylon, polypropylene, polycarbonate and polystyrene.

The injection moulding machine consists of a heated barrel equipped with a reciprocating screw (usually driven by a hydraulic motor), which feeds the molten polymer into a temperature controlled split mould via a channel system of gates and runners. The screw melts (plasticises) the polymer, and also acts as a ram during the injection phase. The screw action also provides additional heating by virtue of the shearing action on the polymer. The pressure of injection is high, dependant on the material being processed; it can be up to one thousand atmospheres.

Most biodegradable polymers can be used for making injection moulded articles. Starch-based polymers are used to manufacture a wide range of items such as pencil sharpeners, rulers, cartridges, combs and toys, plant pots and bones.

One example is the processing of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) into injection moulded articles. It was found that the degree of crystallinity is a result of the processing history during the injection moulding process. In what is known as the fountain flow effect, hot melt flows into a cold mould and quickly forms a frozen layer on the surface of the mould while material in the centre of the sample does not cool as quickly. The difference in cooling rate and orientation causes a difference in the crystallisation between the material close to the surface and material closer to the core. The degree of crystallinity of injection moulded PHBV affects both the properties of the article as well as its biodegradability. This result is also true for many other biodegradable polymers.

PLA is a polymer that may not be well suited to injection moulding. Its rate of crystallisation is too slow to allow cycle times typical of those for commodity thermoplastics such as polystyrene. Stress induced crystallisation that can enhance PLA crystallisation is better suited to processes such as fibre spinning or biaxial orientation of film.

3.11.4 Blow Moulding

Thermoplastics can be moulded into articles by injection moulding or blow moulding.

Blow moulding is the most common process for making hollow articles such as bottles. There are two main types of blow moulding, injection blow moulding and extrusion blow moulding.

Biodegradable Polymers

Injection blow moulding is used for the production of hollow objects in large quantities. The main applications are bottles, jars and other containers. The Injection blow moulding process produces bottles of superior visual and dimensional quality compared to extrusion blow moulding. The process is ideal for both narrow and wide-mouthed containers and produces them fully finished with no flash.

The process is divided into three stages:

1. Injection: The injection blow moulding machine is based on an extruder barrel and screw assembly which melts the polymer. The molten polymer is fed into a manifold where it is injected through nozzles into a hollow, heated preform mould. The preform mould forms the external shape and is clamped around a mandrel (the core rod) which forms the internal shape of the preform. The preform consists of a fully formed bottle/jar neck with a thick tube of polymer attached, which will form the body.

2. Blowing: The preform mould opens and the core rod is rotated and clamped into the hollow, chilled blow mould. The core rod opens and allows compressed air into the perform, which inflates into the finished article shape.

3. Ejection: After a cooling period the blow mould opens and the core rod is rotated to the ejection position. The finished article is stripped off the core rod and leak-tested prior to packing. The preform and blow mould can have many cavities, typically three to sixteen depending on the article size and the required output. There are three sets of core rods, which allow concurrent preform injection, blow moulding and ejection.

For extrusion blow moulding, the blow moulding machine is based on a standard extruder barrel and screw assembly to plasticise the polymer. The molten polymer is led through a right angle and through a die to emerge as a hollow (usually circular) pipe section called a parison.

When the parison has reached a sufficient length a hollow mould is closed around it. The mould mates closely at its bottom edge thus forming a seal. The parison is cut at the top by a knife prior to the mould being moved sideways to a second position where air is blown into the parison to inflate it to the shape of the mould.

After a cooling period the mould is opened and the final article is ejected. To speed production several identical moulds may be fed in cycle by the same extruder unit. The process is not unlike that used for producing glass bottles, in that the molten material is forced into a mould under air pressure.

3.11.5 Injection Stretch Blow Moulding

Injection stretch blow moulding (ISBM) is used for the production of high quality and high clarity containers. PET is the most widely used polymer for injection stretch blow moulding of bottles. During the last two years, there has been a growing interest from brand owners and retailers in the use of PLA for manufacture of stretch blow moulded bottles for short shelf-life products such as mineral water and milk.

The ISBM process is divided into four stages.

1. Injection: Molten polymer flows into the injection cavity via the hot runner block, to produce the desired shape of the preform with a mandrel (the core pin) producing the inner diameter and the injection cavity the outer. After a set time the injection moulds and core pins part and the preform held in a neck carrier is rotated 90°.

Overview of Biodegradable Polymers

2. Conditioning: Because the preform has been cooled in the injection station quickly, it is of varying temperatures throughout its wall thickness. To ensure a good and consistent quality of container, the preform needs a uniform temperature. Heating is employed to achieve this conditioning.

3. Stretching: Once conditioned to the correct temperature the preform is ready for stretching and blowing to the finished shape.

4. Blowing: Once the preform is within the blow mould area the moulds close, a stretch rod is introduced to stretch the preform longitudinally and using two levels of air pressure, the preform is blown circumferentially.

3.11.6 Thermoforming

Thermoforming has close similarities with vacuum forming, except that greater use is made of air pressure and plug assisted forming of the softened sheet. The process is invariably automated and faster cycle times are achieved than in the vacuum forming process. Only thermoplastic sheet can be processed by this method.

The largest application for thermoformed articles is for food packaging. Other industries include toiletries, pharmaceuticals and electronics.

The modern food supply chain uses many forms of thermoformed articles; meat trays, microwave and deep freeze containers, ice cream and margarine tubs, delicatessen tubs, snack tubs, bakery and patisserie packaging, sandwich packs and vending drink cups are just a few of the food related applications. Other non-food applications include manufacturing collation trays, blister packaging and point of sale display trays.

Many thermoplastics can be thermoformed, including polystyrene, polypropylene, APET, CPET, and PVC. EVOH is commonly incorporated into a co-extrusion for its superior barrier properties in food. Co-extrusions of these materials are commonly used to provide precise properties for specific applications.

In terms of biodegradable polymers, PLA is finding growing use for manufacture of thermoformed articles such as single-use disposable cups and trays, particularly for outdoor events. Starch-based biodegradable polymers can also be thermoformed for production of trays and containers for packaging fresh food and convenience food.

The demands of the food packaging industry are for materials which resist the passage of odours, moisture and gases, hence the use of plastics with superior barrier properties.

The majority of thermoforming production is by roll fed machines. Sheet fed machines are used for the smaller volume applications. Larger production units have in house sheet extrusion equipment. Because of the complexities in synchronising sheet extrusion equipment and the thermoforming machines, the two processes can be carried out independently of each other, the extruded sheet being produced in advance of production schedules.

With very large volumes a fully integrated in-line, closed loop system can be justified. The line is fed with plastics raw material, with extruders feeding directly into the thermoforming machine.

The plastic sheet is softened at the heating station. It then indexes to the forming station where the mould tools are located. The forming of the sheet is by a combination of air pressure and male core

Biodegradable Polymers

plugs. Certain designs of thermoforming tool facilitate the cropping of the article being formed within the thermoforming tool. Greater accuracy of cut can be achieved by this method due to the article being produced, and the skeletal (scrap), not having to be re-positioned. Alternatives are where the formed sheet, including skeletal, are indexed to the cropping station.

The high volumes of articles being produced demand that a parts stacker is integrated into the forming machine. Once stacked the finished articles are now packed into boxes for transportation to the end customer. The separated skeletal is either wound onto a mandrill, for subsequent chopping, or passes through a chopping machine which is in line with the thermoforming machine.

3.11.7 Fibre Spinning

The most commonly used commercial processes for making fibres are melt spinning, dry spinning and wet spinning. Melt spinning is the most economical, but can only be applied to polymers that are stable at temperatures sufficiently above their melting point to be extruded in the molten state without degradation. The properties of crystalline polymers can be improved when made into fibre form by the process of orientation or drawing. The result is the increased strength, stiffness, and dimensional stability associated with synthetic fibres.

PLA is the most common type of biodegradable polymer found in fibre form. PLA fibre properties compare favourably with both PET and rayon fibres. Conditions that the polymers are subject to during the spinning process impact on fibre properties such as tensile strength and elongation. Polymer degradation can take place during the melt spinning process even when using dry polymer with less than 0.005% water content. Fibres produced by dry spinning undergo very slight degradation.

References

1. Catia Bastioli, Handbook of Biodegradable Polymers, Rapra Technology Ltd, 2003, 5.

2. Catia Bastioli, Handbook of Biodegradable Polymers, Rapra Technology Ltd, 2003, 11-13.

3. Catia Bastioli, Handbook of Biodegradable Polymers, Rapra Technology Ltd, 2003, 20-22.

4. Catia Bastioli, Handbook of Biodegradable Polymers, Rapra Technology Ltd, 2003, 257-260.

4 The Global Biodegradable Polymers Market

4.1 Introduction

In 2005, there were very few biodegradable polymer production plants operating on a fully commercial scale. NatureWorks LLC, Novamont, Rodenburg Biopolymers and BASF are currently the only major operators with significant production capacity. Nevertheless, the world biopolymers market has shown significant growth during the last five years or so, albeit from a very small base.

The major classes of biopolymer, starch and starch blends, polylactic acid (PLA) and aliphatic-aromatic co-polyesters, are now being used in a wide variety of niche applications, particularly for manufacture of rigid and flexible packaging, bags and sacks and foodservice products. However, market volumes for biopolymers remain extremely low compared with standard petrochemical-based plastics. For example, biopolymer consumption accounted for just 0.14% of total thermoplastics consumption in Western Europe for 2005.

This section reviews the major factors that are driving demand for biodegradable polymers in Western Europe and other major world regions. These include increasing concern for environmental protection, the encouragement of recycling and packaging waste reduction and the development of composting infrastructures in a growing number of countries. There has also been a narrowing in the price differential between biopolymers and standard thermoplastics in recent years, which has encouraged some brand owners to switch in favour of biopolymers.

The section also provides an analysis of biodegradable polymer market size and growth over the last five years for the three major world regions (Western Europe, North America and Asia Pacific), plus forecasts to 2010.

4.2 Market Drivers

4.2.1 Development of Framework Conditions

Biodegradable polymers can make a positive contribution to the conservation of the world’s natural resources and protection of the environment. However, their market potential will only be fulfilled if the required framework conditions are put in place to ensure the necessary investment in technology and production capacity. Framework conditions refer to the development of industry standards and regulatory systems, certification and certification systems that are designed to encourage biodegradable polymer market development.

Biodegradable polymers are one answer to the growing problem of how to dispose of domestic waste materials. Waste management is becoming an increasingly important issue in Western Europe and most other developed countries, especially where there are few sites left that can be used for landfill. Since a high proportion of domestic waste is made of plastics, there is a growing interest in recycling plastics and in producing plastic materials that can be safely and easily disposed of in the environment.

Biodegradable Polymers

Plastic recycling is a requirement of European Union countries. The European Commission Directive 94/62/EC on Packaging and Packaging Waste aims to prevent or minimise the impact of packaging waste on the environment through recovery and recycling targets. In 2002, the EU decided that the material-specific recycling quota for plastics was to be raised from 20% to 22.5%. The mechanical recycling quota for all the different material groups taken together is to be set at a minimum of 55% and a maximum of 80%. All participants in the supply chain, from polymer producers to retailers, have a financial obligation under the directive for meeting the recycling targets.

In December 2005, the EU proposed new legislation to modernise the 1975 Waste Framework Directive, which should give a further boost to the development of biodegradable polymers. The main elements of the proposals are:

• Focussing waste policy on improving the way resources are used;

• Mandatory national waste prevention programmes, which take account of the variety of national, regional and local conditions, to be finalised three years after entry into force of the directive;

• Improving the recycling market by setting environmental standards that specify under which conditions certain recycled wastes are no longer considered waste.

This long-term strategy aims to help Europe become a recycling society that seeks to avoid waste and uses waste as a resource.

EU-wide statistics on waste treatment are available only for municipal waste, which represents about 14% of total waste produced. At present, 49% of EU municipal waste is disposed of through landfill, 18% is incinerated and 27% recycled or composted. There are wide discrepancies between Member States. Some landfill 90% of their municipal waste, others only 10%.

The proportion of recycled municipal waste has been increasing, but this has been offset almost completely by an increase in municipal waste generation. As a result, landfill is only reducing slowly. For example, the amount of plastic waste going to landfill increased by 21.7% between 1990 and 2002, even though the percentage of plastic waste being landfilled dropped from 77% to 62%.

Recycling of municipal waste nearly doubled between 1995 and 2003 and now accounts for 82.3 million tonnes per year. Incineration is slowly increasing and generates energy equivalent to 8 million tonnes of oil.

Biodegradable materials are created specifically with recyclability or disposal in mind. Recycling techniques for post-consumer biodegradable plastic products have two important features, which distinguish them from conventional polymers: their biodegradability or compostability and the use of renewable resources in their manufacture.

The established methods for biological waste recycling of biodegradable plastic products are composting and biogasification. Biodegradable plastics can also be used for energy recovery by incineration and, like conventional polymers, they have a high calorific value. The end products of both processes are carbon dioxide and water. Composting additionally generates biomass, which contributes to the compost’s value as a fertiliser. Incineration generates ash and releases thermal energy. The material cycle can be closed in both scenarios with biodegradable plastics derived from renewable resources.

The choice of recycling option depends primarily on the waste-disposal infrastructure already in place. The choice of recycling route will differ according to product group and region. The goal

The Global Biodegradable Polymers Market

should always be to obtain maximum recycling efficiency, both economically and environmentally,

in compliance with waste legislation requirements.

Composting is the most favoured method for recovery of post-consumer waste biodegradable plastic products, since incineration requires a high calorimetric value and landfill is not suitable for organic materials. Composting is already well established in some European countries, and is being established in others. The Netherlands and Germany are leading countries in the development of a composting infrastructure for biodegradable plastic products. In these countries, more than 95% and 60%, respectively, of all households have access to industrial composting plants. Containers (bio bins) are provided for the collection of organic household refuse. In the EU, organic matter makes up 30-40% of total domestic refuse. In Germany, about 500 plants convert more than six million tonnes of organic refuse into compost.

Biodegradable plastic products must meet stringent quality criteria if they are to be composted. Dedicated standards and certification schemes/tests have been established for verifying the compostability of plastic products.

Compostable polymers must pass compostability test standards that are described in the harmonised European standard EN 13432, introduced in 2000. This standard applies to ‘Packaging’ and is virtually the same as the former DIN V 54900 standard.

The German testing institute, Din Certco, is the body responsible for testing and certifying biodegradable and compostable polymers and products and licenses the use of the corresponding Mark developed by the IBAW, the European Biodegradable Polymers Association and Working Groups.

Certification enables compostable products to be identified by a unique mark and channelled

for recovery of their constituent materials in specially developed processes. The Compostability Mark thus conveys product information to waste-disposal plant operators and product image

to consumers.

A certification can be conducted according to three standards:

• DIN V 54900 ‘Testing of the compostability of plastics’ (replaced by DIN EN 13432.

• DIN EN 13432 ‘Packaging - Requirements for packaging recoverable through composting and biodegradation’ – Test scheme and evaluation criteria for the final acceptance of packaging.

• ASTM D 6400 ’Standard Specification for Compostable Plastics’.

Laboratory tests have to be performed for materials, intermediates and additives. In these tests the chemical properties are checked, the ultimate biodegradability is verified and the disintegration properties are determined. Chemical testing serves to ensure that neither harmful organic substances, such as polychlorinated biphenyl (PCB) and dioxins, nor heavy metals, such as lead, mercury and cadmium, pass into the soil via the compost.

The method specified for the testing of biodegradability serves to verify the complete degradation of the materials within the processing period of normal composting plants. An ecological non- toxicity test that is also prescribed ensures that the plastics used have no adverse effect on the quality of the compost. Additionally the maximum compostable layer thickness is determined. If the results of the tests are in conformity with the standard(s) and/or the certification scheme, the material, intermediate or additive is registered as biodegradable and compostable.

Biodegradable Polymers

Products that have been manufactured from registered materials, intermediates and additives, may be certified, if they meet the maximum compostable layer thickness of the used materials or intermediates.

Verification tests are performed in order to verify that the same base materials as those declared on application for certification are being used. For this purpose, infrared spectra are recorded and compared.

The biodegradable plastics industry initiated the development of standards to protect biodegradable plastics suppliers from imitation products. The term ‘compostable’ could not be legally protected and can be abused by other product suppliers. For example, manufacturers of standard polymers, such as polyethylene, offer what they term ‘compostable grades’ for production of plastic bags. None of the additive containing PE products has so far provided compelling proof of compostability as set out in the stringent standards criteria.

Polymeric materials whose organic constituents undergo complete biological degradation are termed biodegradable. Biodegradation is a process caused by biological activity that, accompanied by changes to the chemical structure of the material, leads to naturally occurring metabolic end products. The ambient conditions and the rate of biodegradation have to be determined in standardised test methods.

The very fact that a material is biodegradable is not good enough on its own when it comes to industrial processes for recycling biodegradable products. Much more important is verifiable degradation within the typical timeframe of the method. Accordingly, the mentioned DIN standard defines compostability as the property of a polymeric material to degrade during a composting process. ‘Biologically degradable’ is therefore by no means equivalent to ‘compostable’.

Since the term ‘compostable’ could not be protected by legal means and biodegradable plastic products cannot be distinguished from conventional polymers by their appearance, a certification and identification process was created with the support of the German Ministry for Consumer Protection, Agriculture and Forests.

The certification programme for compostable biodegradable plastic products has been set up by experts responsible for waste recycling and compost quality assurance. The members are as follows:

• Bundesgütegemeinschaft Kompost (German association for compost quality assurance)

• Bundesverband der deutschen Entsorgungswirtschaft (Association of the German waste- management industries)

• Bundesverband Humus- und Erdenwirtschaft e.V. (German association for humus and soil application)

• Bundesvereinigung der kommunalen Spitzenverbände (Association of German cities and municipalities)

• Deutscher Bauernverband (German farmers association)

• Industrieverband Kunststoffverpackungen (Association for plastic packaging)

• IBAW, the European Biodegradable Plastics Association

The Global Biodegradable Polymers Market

Industry associations have recognised the need for quality assurance measures as a means of counteracting the threats posed to the biodegradable plastics industry by other materials claiming to be biodegradable and compostable. IBAW has worked alongside the Biodegradable Polymers Institute (BPI) in the USA and the Biodegradable Polymer Society (BPS) in Japan to establish a harmonised certification and labelling system at the international level.

In 2005, the four leading European biodegradable plastics material suppliers: BASF, NatureWorks, Novamont and Rodenburg Polymers, have also agreed to submit their packaging materials and products for certification by Din Certco under EN 13432, and label their packaging products with the compostability logo to better inform consumers and retailers.

The biodegradable polymers industry is also slowly receiving more political support to bolster market development.

The amended German Packaging Ordinance in December 2004, makes special provision for certified bio-packaging, i.e., packaging proven to be compostable. Up to 2012, certified biodegradable plastic packaging products need not be accepted as returns, nor are they subject to recycling quotas. The German Federal Ministry of Consumer Protection, Food and Agriculture has also announced that the national budget allocated to research, development and market launches of renewable materials for 2005 has been virtually doubled to 54 million.

In October 2005, the French National Assembly also boosted the prospects for biopolymers with a vote to ban production and use of non-biodegradable plastic bags from 2010. Food and industrial packaging will not be affected. The legislation is designed not only to combat littering but to provide farmers with a new source of income, growing starch-rich maize for packaging. France’s environment ministry estimates that some 15 billion plastic carrier bags, representing 60,000-80,000 tonnes of polymer are circulated in the country annually and that 120 million bags are discarded rather than being recycled.

4.2.2 Development of a Composting Infrastructure

For biodegradable polymers to achieve their full market potential, they should add greater functionality and productivity for the end user, if the relatively high prices are to be justified. So far there has been very limited development of an infrastructure for composting and thus the true benefits from using biodegradable polymers are not being realised.

Perhaps one of the biggest hurdles for the adoption of biodegradable and compostable materials has been the lack of kerb-side collection and municipal composting facilities, particularly in the USA and parts of Europe. Municipal composting would ‘complete the circle’ for materials such as biopolymers, which start as natural renewable resources and degrade back to useable compost material. The wider development of a composting infrastructure would permit a realisation of the marketing benefits that seems to drive the adoption of sustainable materials.

Over the last few years, European legislation has become the key driver for national and regional policy on composting. The targets for diverting biodegradable municipal waste from landfill set out in the European Landfill Directive (EC/31/1999) have led to significant developments in composting infrastructures across Europe.

The landfill directive is one of the most important environmental directives the European Parliament has dealt with in recent years. It marks the beginning of a major shift in waste management practice

Biodegradable Polymers

in Europe. For the public it represents the end of an era in which people have given very little thought to what happens to the waste they produce. Seven countries currently landfill more than half of the municipal waste they produce. These are Austria, Finland, Greece, Ireland, Italy, Spain and the United Kingdom. For these countries in particular, this directive poses a major challenge to the so-called ‘throwaway’ culture.

The three key features of the directive are firstly the promotion of the move away from landfill to more environmentally acceptable alternatives. Secondly, the directive calls for the establishment of European Union wide standards for proper management of landfills. Thirdly, it should result in the discouragement of the transport of waste across frontiers by removing the disparities between the practices and prices relating to landfill in the Member States.

In the UK, The Waste and Emissions Trading (WET) Act 2003 provides the framework for the Landfill Allowance Trading Scheme (LATS) designed to meet the diversion targets laid down in Article 5(2) of the Landfill Directive. The UK targets have been divided up between England, Wales, Scotland and Northern Ireland, and the relevant government body in each nation is responsible for dividing the targets between local authorities who manage disposal.

LATS is a market-based mechanism that introduces progressively tighter restrictions on the amount of paper, food and garden waste that authorities can landfill. Local authorities are allocated an annual landfill allowance for municipal biodegradable waste. They are under a duty not to exceed this allowance and face punitive fines for every tonne landfilled above the total amount of allowances they hold. EU fines imposed on the UK for failure to meet the targets will be split between local authorities in direct proportion to their contribution in breaching the targets.

The devolved nations have each set incremental recovery, recycling and composting targets to improve performance in the management of household waste. The national targets are divided between local authorities depending on individual performance. In England the aim is to achieve a combined recycling and composting rate of 33% of household waste by 2015, in Wales the target is 40% recycling and composting of municipal waste by 2010 (with a minimum of 15% from composting), Scotland has set municipal waste targets of 35% recycling and 20% composting by 2020, and Northern Ireland has set a target for household waste of 25% recycling and composting by 2010.

Against this backdrop of waste strategy targets, the Household Waste Recycling Act (2003) requires all local authorities in England to provide kerbside collections for all householders for a minimum of two materials by 2010. Under the Act kerbside collections of food waste as well as green waste will count as a type of recyclable (providing the waste collection authority does not levy a charge for green waste collections).

These national targets aim to push waste further up the waste management hierarchy. Whilst improving the performance levels for dry recyclables will continue to be important for authorities, the introduction of LATS together with the ‘composting’ element of the waste strategy targets is likely to focus efforts on biodegradable municipal wastes.

In Europe, Germany and the Netherlands lead the way for separate collection of organic municipal waste for composting. In Germany, source separation of organic residues from households, gardens and parks (biowaste) is one of the main measures in waste management. The participation rate in source separation of biowaste is 70-75% of all German households. In the Netherlands, over 90% of households were involved in the separate collection system for organic waste.

The Global Biodegradable Polymers Market

In 2003, the Dutch regulations agreed to permit biodegradable materials in the ‘green bins’ for professional composting. ‘Green bins’ are part of a system for separating household waste from ‘green’ or recyclable waste. As a first step, only biodegradable shopping bags will be allowed in the green bins. If the scheme proves a success, then retailers will be allowed to put products that have passed their sell by date direct into the green bins, without separating the content of the packaging, thus saving on costs.

4.2.3 Pricing Trends

Recent upswings in the cost and declining availability of standard petroleum-based resins have brought biodegradable polymers to a price-competitive level versus petrochemical based polymers. Commodity resin prices have climbed steadily since 2003 as oil and natural gas prices have surged. During the period 2003-2005, average PP homopolymer prices and general purpose polystyrene prices have jumped by over 31%, LDPE film grade prices have gone up by 34.5% and bottle-grade PET prices have increased by nearly 18%.

Table 4.1 shows the changes in average standard thermoplastic prices for the years 2003-2005 in Western Europe.

Table 4.1 Average standard thermoplastic prices 2003-2005, Western Europe (/tonne)

 

2003

2004

2005

% Change

2003-2005

LDPE

851

1022

1145

34.5

PP homo

798

898

1051

31.7

PS crystal

882

1101

1157

31.2

PET bottle grade

1054

1146

1241

17.7

At the same time, prices for three major types of bio-based resins, starch-based biopolymers, polylactic acid (PLA) and aliphatic aromatic co-polyester, have dropped considerably over the last three years.

The price of starch-based biopolymers has come down considerably over the last three years as production volumes have increased, more efficient production processes have been deployed and lower cost raw materials have been found. In 2003, the average price of starch blends was around

3.0-5.0 per kg. In 2005, the average price range of starch blends was down to 1.5-3.5 per kg, with an average price close to 1.75 per kg.

Similarly, PLA biodegradable polymer prices have fallen sharply over the last five years since the polymers were first commercialised. NatureWorks PLA is now available at prices between 1.37-2.75 per kg compared to a price range of 3.0-3.5 per kg three years ago. NatureWorks PLA has been price competitive with PET for example over the last twelve months as PLA manufacturing scale has increased and process improvements were made alongside the recent sustained higher levels of PET pricing.

Biodegradable Polymers

The price of synthetic biopolymers has come down a little during the last three years. In 2005, the average cost of an aliphatic aromatic co-polyester biopolymer was between 2.75-3.65 per kg. In 2003, the average price of aliphatic aromatic co-polyesters was around 3.5-4.0 per kg. Prices are expected to fall further over time as production volumes increase and unit costs fall.

Historically, pricing had been the biggest barrier to biodegradable polymer market development. However, growing volumes of production and the development of new technology should further allow bio-based resin makers to reduce costs. Using materials such as corn stover, wheat straw and rice straw, which remain in fields after crops are harvested, as resin feedstock, could also increase productivity and economic performance.

4.2.4 Growth in Pre-Packaged Food Sales

The inexorable rise in pre-packaged disposable meals means that food manufacturers and packagers are increasingly being targeted to improve their environmental performances.

Demographic trends are also encouraging growth in pre-packaged food sales. Datamonitor statistics for example, show that more than one-third of European consumers live alone and are spending

140 billion a year on food, drinks and personal care products. Single people spend 50% more per

person on consumer-packaged goods than a two adult household. Such trends underline why concern about the environmental impact of food packaging has never been greater.

4.2.5 Consumer Preference for Sustainable Packaging

Consumers are in favour of a sustainable product development such as biodegradable plastics. In 2001, a survey of 600 people in the town of Kassel, Germany was conducted to determine the acceptability of biodegradable packaging to consumers. The study revealed that about 90% considered the idea of replacing conventional plastic packaging by compostable packaging to be either good or very good. 80% of customers using biodegradable packaging classified the quality as either good or very good, and 87% said they would buy it again.

The results of the Kassel project show that, in any event, one-third of consumers would be prepared to pay a surcharge, as much as 0.15 for a carrier bag, instead of the current 0.10, provided it were compostable. For a biodegradable yoghurt tub, they would willingly pay an extra 0.05. However, it was found that a higher surcharge would deter sales.

Consumers also found the idea of potatoes wrapped in potato-based packaging a fascinating concept and many consumers appreciated that it represented progress. This did not just apply to those consumers who usually buy organic produce. There are no doubt good opportunities for companies to differentiate their products from those of the competition.

There is also growing evidence that brand owners and retailers are favouring greater use of sustainable packaging based on biodegradable materials rather than conventional plastics. Sustainable packaging presents an opportunity for manufacturers and retailers to differentiate their products and to present a more environmentally-friendly image to consumers. Biodegradable packaging is a natural fit with organic products, which is a fast growing market. A number of retailers are now offering organically grown fruit and vegetables, and other produce, in biodegradable packaging.

The Global Biodegradable Polymers Market

4.2.6 Product and Technology Development

During the last few years, there has been a stream of new product and technology development by leading biodegradable polymer suppliers that have opened up new markets and potential applications.

NatureWorks is developing a new generation of PLA that can be used for microwavable packaging. The company has also announced results of research that showed bottles could be used to package oxygen sensitive food and beverages using barrier-enhanced PLA in the future.

Hycail announced the launch of a new PLA material which can withstand temperatures over 200 °C without distortion. It can also be microwaved with fatty and liquid foods, without distortion or stress cracking.

Toray Industries has developed a new technology for manufacture of PLA flexible film that has succeeded in containing the occurrence of bleeding out when faced with changes in temperature or pressure and displays highly stable flexibility while not losing any of the superior features of PLA such as transparency, heat resistance, and biodegradability. Traditionally, a low-molecular-weight liquid plasticiser addition method has been used for achieving flexible PLA films.

In the synthetic biodegradables sector, BASF expanded its Ecoflex-brand with Ecovio, a blend of NatureWorks PLA and Ecoflex.

In the starch sector for example, Stanelco is understood to be developing a new starch-based biopolymer that it claims will undercut PET and PP prices, while offering a similar ease of processing in both bottle blowing and thermoforming processes.

Developments in additive formulations are also helping to improve processing efficiencies for biodegradable polymers. PolyOne for example, introduced a new range of colour and additive masterbatches for biodegradable resins for the European market in 2005.

4.3 Market Development and Structure

Global production capacity for biodegradable polymers has grown dramatically since the mid 1990s. In 1995, production was mainly on a pilot-plant basis with total worldwide capacity amounting to no more than 25-30,000 tonnes. In 2005, global capacity for biodegradable polymers was around 360,000 tonnes. Biopolymers based on renewable resources (starch and PLA and including loose- fill packaging) accounted for around 300,000 tonnes with synthetic biopolymers accounting for approximately 60,000 tonnes. Based on announced projects, total production capacity is set to almost reach 600,000 tonnes by 2008.

Polylactide (PLA) is the leading polymer type among biodegradables with global production capacity for this material amounting to about 250,000 tonnes per annum in 2005. Starch-based polymer capacity is approaching 60,000 tonnes per annum.

In 2006, there are around 30 major companies worldwide that are actively involved in developing biodegradable plastic materials. The synthetic biopolymers market is dominated by large, global and vertically integrated chemical companies such as BASF, DuPont, and Mitsubishi Gas Chemicals. The starch and PLA sectors contain mainly specialist biopolymer companies such as Novamont, NatureWorks, Rodenburg Biopolymers and Biotec, which were specifically established purely to develop biodegradable polymers.

Biodegradable Polymers

Table 4.2 shows the major biodegradable polymer suppliers by product type for 2005.

Table 4.2 World biodegradable polymers market, 2005 – major suppliers by product type

 

Starch

PLA

PHA

Synthetic

BASF

     

X

BIOP

X

     

Biomer

 

X

X

 

Biotec

X

     

Cereplast

 

X

   

Daicel Chemical

     

X

Dainippon

     

X

DuPont

     

X

Earth Shell

X

     

FkuR

 

X

 

X

Grenidea

X

     

Hycail

 

X

   

IRe Chemical

     

X

Metabolix

   

X

 

Mitsubishi Gas Chemical

     

X

Mitsui Chemical

 

X

   

NEC

 

X

   

NNZ

X

     

NatureWorks

 

X

   

Novamont

X

   

X

Plantic

X

     

Polyscience

   

X

 

Procter & Gamble

   

X

 

Rodenberg

X

     

SK Chemical

     

X

Showa

     

X

Solvay

     

X

Stanelco

X

X

   

Toyota

 

X

   

The leading biodegradable polymer suppliers are Novamont, NatureWorks, BASF and Rodenburg Biopolymers, which together represent over 90% of the European market for biodegradable plastics.

The Global Biodegradable Polymers Market

At the moment, there are a growing number of biodegradable polymers performing well in niche applications. Many of these materials can be even more cost competitive in the future compared to petroleum-based resins including PET, PE, and PP as suppliers develop better material properties that can lead to thinner films or lower processing costs.

In terms of the product life cycle analysis, a new product or polymer would generally require about thirty years from the research and development stage before becoming a commodity product when millions of tonnes are produced annually for mainstream application. In 2005, the biodegradable plastics industry has about fifteen to twenty years of development time behind it and has now reached the market introduction stage.

During the last ten years or so the main focus of research and development activity for companies involved in the biopolymers market was on improving the technology and the products in readiness for full commercialisation. Now, a significant number of products are commercially available and the emphasis has switched to the end user and developing markets and applications.

Brand owners and supermarkets as well as a consumer, will have a key role to play in the growth of this industry over the next five to ten years. Buyers must begin to understand the marketing value of sustainable materials such as greater energy independence, cleaner soil, less air pollutants, and less impact on global warming. Only then will they endorse this biopolymers’ movement and invest in educating consumers in the value to society of these materials. It is education and awareness along with the cost and performance improvements that will take sustainable materials out of their niche market status and into mainstream applications.

Production costs for biopolymers still remain high because of the relatively low volumes being produced and the profitability of biodegradable plastics products remains low. Hence, volumes must be increased if unit costs are to fall and profitability is to improve. The development of new applications will be crucial to achieving higher production volumes and generating the profitability needed for further investment in production capacity.

While the cost of some biodegradable plastics are currently higher than most conventional polymers, from a marketing perspective, it is important not only to consider the material cost, but also all associated costs, including the costs of handling and disposal, which are of course lower for biodegradable plastics. Hence, marketing of biodegradable plastics products is most successful when their cost savings and material advantages are exploited to the full. Also, users of biodegradable plastics can differentiate themselves from the competition by demonstrating how innovative and proactive they are for the benefit of the environment.

4.4 The Global Biodegradable Polymers Market Forecast

Over the last five years, global consumption of biodegradable polymers has shown strong growth. Demand has been fuelled by growing public demand for sustainable packaging materials, growth in composting infrastructures, the introduction of a wider variety of biodegradable polymers, product improvements and a narrowing of the price differential between biopolymers and petrochemical- based plastics.

In 2005, the global biodegradable plastics market tonnage is 94,800 tonnes (including loose-fill packaging) compared with 28,000 tonnes in 2000. In 2010, market tonnage is forecast to reach 214,400 tonnes, which represents a compound annual growth rate of 17.7% during the period

Biodegradable Polymers

2005-2010. Excluding loose-fill packaging, which is a relatively more mature sector for starch-based biodegradable polymers, global market tonnage in 2005 is 71,700 tonnes and the compound annual growth rate for the period 2005-2010 is projected to be 20.3%.

Table 4.3 shows global consumption of biodegradable polymers by world region for the years 2000, 2005 and forecast for 2010.

Table 4.3 Global consumption of biodegradable polymers, 2000, 2005 and 2010 (’000 tonnes)

2000

2005

2010

% CAGR

2005-2010

Western Europe

15.5

55.7

129.4

18.4

North America

6.7

21.3

46.5

16.9

Asia Pacific

5.8

17.8

38.5

16.7

28.0

94.8

214.4

17.7

Western Europe is the leading market for biodegradable polymers with 59% of market volumes in 2005, followed by North America with 22% and Asia Pacific with 19%. Western Europe is also forecast to show the fastest growth rate for biodegradable polymers over the period

2005-2010.

Figure 4.1 shows percentage share of global biodegradable polymer consumption by geographic region for 2005.

polymer consumption by geographic region for 2005. Figure 4.1 Percentage share of global biodegradable polymer

Figure 4.1 Percentage share of global biodegradable polymer consumption by geographic region for 2005

Starch-based materials represent the largest class of biodegradable polymer with 44,800 tonnes (including loose-fill foam packaging) consumed in 2005. Excluding loose-fill, starch-based materials amounted to 21,700 tonnes in 2005. Polylactic acid (PLA) is the second largest material class with 35,800 tonnes in 2005, followed by synthetic aliphatic-aromatic copolyesters with 14,000 tonnes. The embryonic PHA category amounts to around 250 tonnes.

The Global Biodegradable Polymers Market

Figure 4.2 shows percentage share of global biodegradable polymer consumption by polymer type for 2005.

biodegradable polymer consumption by polymer type for 2005. Figure 4.2 Percentage share of global biodegradable polymer

Figure 4.2 Percentage share of global biodegradable polymer consumption by polymer type, 2005

All classes of biodegradable polymers are projected to show substantial growth during the next five years. Of the material classes with existing commercial applications, PLA will grow the fastest with a compound annual growth rate of 20.1% for the period 2005-2010. Synthetic types will grow by 18.6% per annum and starch-based polymers will grow at 14.8% per annum. However, excluding loose-fill packaging, which is growing at a lower rate than other applications, starch is forecast to grow by 20.6% per annum over the next five years. The PHA sector, which started from virtually a zero base in 2005, is projected to grow at close to 60% per annum.

Figure 4.3 shows percentage share of global biodegradable polymer consumption by end user sector for 2005.

polymer consumption by end user sector for 2005. Figure 4.3 Percentage share of global biodegradable polymer

Figure 4.3 Percentage share of global biodegradable polymer consumption by end user sector, 2005

Biodegradable Polymers

In terms of end use markets, packaging (including rigid and flexible packaging, paper coating and foodservice) is the largest sector with 39% of total market volumes in 2005. Loose-fill packaging is the second largest sector with 24%, followed by bags and sacks with 21%. Fibres or textiles, is an important sector for PLA, and accounts for 9% of total market volumes. Others include a wide range of very small application areas, the most important of which are agriculture and fishing, medical devices, consumer products and hygiene products.

4.4.1 Western European Biodegradable Polymers Market Forecast

Western Europe is by far the biggest market for biodegradable polymers accounting for 59% of world consumption in 2005. The Western European market for biodegradable polymers has been driven more by regulation than other world regions such as the USA and Japan. These include the European Union directives on packaging waste and landfill which aim to divert a growing amount of packaging waste towards recycling and composting. Europe has also benefited from some of the world’s leading biodegradable producers such as Novamont, Rodenburg Biopolymers and BASF being based in the region.

Table 4.4 shows Western European biodegradable polymer consumption by polymer type for the years 2000, 2005 and 2010.

Table 4.4 Western European biodegradable polymer consumption by polymer type, 2000, 2005 and 2010 (’000 tonnes)

       

% CAGR

2000

2005

2010

2005-2010

Starch

10.3

29.9

62.1

15.8

PLA

3.7

19.0

50.5

21.6

Synthetic

1.5

6.7

15.8

21.0

PHA

0.0

0.1

1.0

60.0

 

15.5

55.7

129.4

18.4

In 2005, Western Europe consumed 55,700 tonnes of biodegradable polymers compared with 15,500 tonnes in 2000. In 2010, Western European consumption of biodegradable polymers is forecast to reach 129,400 tonnes, which represents a compound annual growth rate of 18.4% during the period

2005-2010.

Figure 4.4 shows the percentage share of Western European biodegradable polymer consumption by polymer type for 2005.

Starch is the most widely used biodegradable polymer in Western Europe accounting for 54% of market tonnage in 2005. PLA accounts for 34% with synthetics making up the remaining 12% of market volumes. Starch, excluding loose-fill packaging, is projected to be the fastest growing biopolymer in Western Europe for the period 2005-2010 with a compound annual growth rate of

The Global Biodegradable Polymers Market

The Global Biodegradable Polymers Market Figure 4.4 Percentage share of Western European biodegradable polymer

Figure 4.4 Percentage share of Western European biodegradable polymer consumption by polymer type, 2005

just over 22%. PLA is also forecast to grow close to 22%, with synthetic biopolymers growing at a slightly lower rate of 18.7% per annum.

Figure 4.5 shows percentage share of Western European biodegradable polymer consumption by end use sector for 2005.

polymer consumption by end use sector for 2005. Figure 4.5 Percentage share of Western European

Figure 4.5 Percentage share of Western European biodegradable polymer consumption by end use sector, 2005

Packaging is the largest sector for biodegradable polymers in Western Europe accounting for 37% of market tonnage on 2005. Rigid packaging applications have been around in Europe longer than the film packaging market, which started in UK in 2001-2002, and was followed by Italy, Switzerland, Belgium and the Netherlands. Bags and sacks is another significant European market for biopolymers representing 21% of total consumption. Biowaste collection bags are

Biodegradable Polymers

used in nearly all EU countries and have strong growth potential. Loose-fill packaging is rather a more mature sector and future growth trends are expected to be less than 10% per annum over the next five years. Agricultural mulch film is the most important sector included under the ‘others’ category. Mulch film is mainly used in France, Spain, Italy and Benelux, and has strong growth potential.

4.4.2 North American Biodegradable Polymers Market Forecast

North America has lagged well behind Western Europe in terms of biodegradable polymer market development. Traditionally, there has not been the same degree of urgency to address the issue of waste disposal through landfill in North America because of its enormous landmass. Government and consumer attitudes towards recycling of packaging waste and environmental protection have also militated against market development of sustainable materials.

However, attitudes are slowly changing. During the last few years there have been a number of positive trends that are encouraging biodegradable polymer development. These include:

• Growth of the composting infrastructure with more municipalities coming on line in both the US and Canada.

• More institutions such as schools looking at food waste diversion from landfill.

• Tipping fees for landfill are rising, especially in more populated areas of the country.

• The rising cost of petrochemical-based polymers over the last two years.

• Better understanding among foodservice suppliers that there is a market for compostable materials.

• Major retailers and food manufacturers have opted for biodegradable packaging in 2005. For example, Wal-Mart Stores selected NatureWorks PLA to manufacture containers for herbs and other products, while Del Monte Fresh Produce increased its use of NatureWorks PLA for packaging fruit.

Table 4.5 shows North American biodegradable polymer consumption by polymer type for the years 2000, 2005 and 2010.

Table 4.5 North American biodegradable polymer consumption by polymer type, 2000, 2005 and 2010 (’000 tonnes)

       

% CAGR

2000

2005

2010

2005-2010

Starch

2.8

8.0

14.0

11.9

PLA

2.7

9.6

22.6

18.7

Synthetic

1.2

3.6

8.4

18.4

PHA

0.0

0.1

1.5

71.0

 

6.7

21.3

46.5

16.9

The Global Biodegradable Polymers Market

In 2005, North American biodegradable polymer consumption was 21,300 tonnes against 6,700 tonnes in 2000. In 2010, biodegradable polymer consumption is projected to reach 46,500 tonnes, which represents a compound annual growth rate of 16.9% during the period 2005-2010.

Figure 4.6 shows percentage share of North American biodegradable polymer consumption by product type for 2005.

biodegradable polymer consumption by product type for 2005. Figure 4.6 Percentage share of North American biodegradable

Figure 4.6 Percentage share of North American biodegradable polymer consumption by type, 2005

PLA, with 45% of total volume, is the most widely used biodegradable polymer in North America, followed by starch with 38% and synthetics with the remaining 17%. PLA is also expected to show the fastest rate of growth over the forecast period with volumes increasing at a compound annual growth rate of 18.7%. Synthetic biodegradable polymer growth is not far behind at 18.5%.

Figure 4.7 shows percentage share of North American biodegradable polymer consumption by end use market for 2005.

polymer consumption by end use market for 2005. Figure 4.7 Percentage share of North American biodegradable

Figure 4.7 Percentage share of North American biodegradable polymer consumption by end use market, 2005

Biodegradable Polymers

Packaging is the largest application area for bioplastics in North America with 41% of total volumes in 2005. Other significant markets are loose-fill packaging foam and bags and sacks.

4.4.3 Asia Pacific Biodegradable Polymers Market Forecast

Japan is the largest consumer of biodegradable polymers in the Asia Pacific region, followed by Australia and New Zealand, with Taiwan, South Korea, Singapore and China, some way behind in terms of market development.

Taiwan and Japan probably offer the best prospects for growth in biodegradable plastics over the next five years.

The Taiwanese government has responded to the growing problems that are being caused to the environment by the disposal of waste plastic items by introducing new environmental policies banning the use of disposable plastics starting with petroleum-based plastic shopping bags and disposable plastic tableware.

In Japan, the Biodegradable Plastics Society (BPS) was set up in 1989 to establish technology of biodegradable plastics (GreenPla), to lead extensive, commercial use of GreenPla, to develop evaluation methods of GreenPla and certify GreenPla products.

During the period 2003-2005, the BPS has certified a large number of GreenPla products in Japan. Tables 4.6, 4.7, 4.8 and 4.9 show certified GreenPla products in the fields of daily use, packaging, agriculture and horticulture and foodservice.

Table 4.6 Certified GreenPla products (daily products)

Product/trade name

BDP type

Producer

“CHIKYU-MARU” drain net

PLA

Yamadai

“Nature Green” straw

PLA

WEI MON INDUSTRY

Garbage bag

PBAT

SARUKAWA

Drawstring trash bag

PBSA

Arke Planning

Calender frame

PLA

Fuji Chemicals

Case for desk calendar (sheet type)

PLA

Arke Planning

Ruler

PLA

Arke Planning

Envelope with window

PLA

Arke Planning

Clip

PLA

Arke Planning

Clear file

PLA

Arke Planning

Card

PLA

Arke Planning

Fan

PLA

Arke Planning

Biodegradable garbage bag

PETS

J Film

“CHIKYU-MARU” biodegradable drain net

PLA

Yamadai

Biodegradable daily bag

PBSA

Ohkura Industrial

Garbage bage for business use

PBSA

Asahi Kasei Life & Living

The Global Biodegradable Polymers Market

Table 4.6 Certified GreenPla products (daily products) Continued

Product/trade name

BDP type

Producer

“NAMANAMA 4444” (Trash bag)

PLA

Towakako

Compost bag

PBSA

KIRA SHIKO

Biodegradable garbage bag

CL-BS copolymer

Tohcello

“NAMANAMA” (Trash bag)

PLA

Towakako

Trash bag (“ECOLOME LBS”)

PBSA

Ohkura Industrial

“PAPERMAC” compost bag CL

CL-BS copolymer

Kitamura Chemicals

Compost bag

PESA

KIRA SHIKO

Compost bag

BS-LA copolymer

KIRA SHIKO

Shoehorn

PBS

Daito Mechatronics

Biodegradable garbage bag, shopping bag

PBAT

Tohcello

Fashion bag with cotton string

PBAT

Ohkura Industrial

Garbage bag

BS-LA copolymer

Kuki-Miyashiro

“BRIGHTON” shopping bag

PLA

HORIAKI

“BRIGHTON” trash bag

PLA

HORIAKI

Bags

PCL

Green Environmental Technology

“TERRAMAC film” trash bag

PLA

Unitika Trading

“ECO&B” handy loupe

PLA

NTT Neomeit Hokuri

Biodegradable straw

PLA

Watanabe Kogyo

Pland-derived neck strap

PLA

NAX

“PEACH COAT” LR series synthetic paper for printing

PLA

NISSINBO Industries

“TERRAMAC” trash bag JM

PLA

Unitika

Biodegradable garbage bag for business use (GB series)

PBAT

Asahi Kasei Life & Living

Table 4.7 Certified GreenPla products (packaging)

Product/trade name

BDP type

Producer

“TERRAMAC” Film

PLA

Unitika

Plant-derived opaque sheet

PLA

SEKISUI SEIKEI

String bag for booklet

PBAT

SARUKAWA

“KANEPEARL” PLA foam (Packaging materials)

PLA

KANEKA

“KANEPEARL” PLA foam (Container for food)

PLA

KANEKA

Shrink label for heat shrinkable cap

PLA

Dai Nippon Printing

“Nature Green” packaging bags

PBAT

WEI MON INDUSTRY

“Nature Green” film

PBAT

WEI MON INDUSTRY

Biodegradable Polymers

Table 4.7 Certified GreenPla products (packaging) Continued

Product/trade name

BDP type

Producer

“Nature Green” NCP0002 sheet

PLA

WEI MON INDUSTRY

“Nature Green” PESC101 sheet

PLA

WEI MON INDUSTRY

“BIPLA TAPE”

PBAT

Shinano kagaku

Heat shrink cap seal

PLA

Fuji Seal

Biodegradable packaging bag

PLA

Vendor service

Over wrapping film for vegetables and fruits

PLA

Taiyo Kogyo

Container for vegetables and fruits

PLA

Taiyo Kogyo

Bag for vegetables and fruits

PLA

Taiyo Kogyo

Antifog bag for vegetables & fruits (flexible type)

PBAT

Office Media

Flexible bag for electronic appliance parts

PLA

Office Media

“NAI-SMELL”PLA alumina metalizing transparent high-barrier film

PLA

Office Media

“NAI-SMELL” PLA aluminum metalizing high-barrier film

PLA

Office Media

Nonslip clothing bag

PLA

Office Media

“NAI-SMELL” PLA antifog bag for vegetables & fruits (flexible type)

PLA

Office Media

“NAI-SMELL” PLA antifog bag for vegetables & fruits (rigid type)

PLA

Office Media

Biodegradable shopping bag

PBSA

KIRA SHIKO

Biodegradable film

PLA

SEKISUI JUSHI

Tablet case

PLA

Toppan Printing

“POPURAN GREEN”

PETS

Yamato

Heat shrink label

PLA

Fuji Seal

Coating film

PLA

MIKASA INDUSTRY

Over wrapping film

PLA

Taiyo Kogyo

“BIOPLUS” laminate film

PLA

Asahi Kasei Life & Living

“DOLON NK-A”

PLA

Aicello Chemical

Bags for foods

Starch

Dai Nippon Printing

Bags for foods

PBAT

Dai Nippon Printing

Packaging materials for newspaper & magazine to recycle

PBSA

MATSUMOTO GOUSEI

“TERRAMAC” sheet HS

PLA

Unitika

“ECO&B” bag for calendar

CL-BS copolymer

NTT Neomeit Hokuriku

Biodegradable thin film

PLA

Yao Qing Biotechnology

Biodegradable bag

PLA

Yao Qing Biotechnology

Expanded heat resistance sheet

PLA

Yao Qing Biotechnology

Heat resistance sheet

PLA

Yao Qing Biotechnology

Transparent food packaging

PLA

Yao Qing Biotechnology

The Global Biodegradable Polymers Market

Table 4.7 Certified GreenPla products (packaging) Continued

Product/trade name

BDP type

Producer

PLA transparent sheet

PLA

Yao Qing Biotechnology

Opaque sheet

PLA

SEKISUI SEIKEI

Translucent sheet

PLA

SEKISUI SEIKEI

“KANKYO” bag B

PLA

UNITIKA FIBERS

“TERRAMAC” sheet SS

PLA

Unitika

Package for novelties

PLA

Tohcello

“PALGREEN LC” flower wrap

PLA

Tohcello

Package for pocket tissue paper

BS-LA copolymer

Tohcello

 

Starch-based

 

“MATER-FOLIO” (packaging film)

copolyester

ASAHI SOGYO