bioplastics MAGAZINE 03/2013 by bioplastics MAGAZINE

ISSN 1862-5258

May / June

03 | 2013

Basics

Highlights

Succinic acid | 60

Injection Moulding | 16 PLA Recycling | 40

Cover-Story

bioplastics

magazine

Vol. 8

Toy blocks | 20

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Editorial

dear readers

Michael and Jenny (Covergirl 05/2011)

bioplastics MAGAZINE has already reported a couple of times about the PLA beverage cups that are collected and recycled at large festivals, sport events or rock concerts. “So why not do it myself?” I thought earlier this year. During a rather small local festival in my home town of Mönchengladbach in Germany I succeeded in convincing the organizers to sell beer in PLA cups (Ingeo™ cups supplied by Huhtamaki). And just like at the other festivals or concerts, the guests were offered a free drink for each ten returned cups. The collected cups will be sent to Purac to be recycled during one of the next uses of the Perpetual Plastic Project’s recycling machine (see p. 54). The festival is a typical German Schützenfest (see http://bit.ly/Y1SmVP for an explanation), and this year I was one of the two Ministers to the King of Marksmen, wearing a traditional red hussar’s uniform. Now… after combining job and leisure… back to business: And back to recycling of PLA, which is one of the highlights in this issue, even though we could not obtain the latest news about the future of the chemical recycling system LOOPLA in time to include it. The project will be continued by Futerro after Galactic decided to orient its development towards more specific solutions for the food and pharmaceutical sectors, and we still offer our readers a lot of other articles and news around the recycling of PLA. We will certainly keep you updated on the future of LOOPLA… The other editorial focus is on injection moulding of components for use in durable applications. Because durable applications have become an increased focus of attention in the bioplastics world, we also decided to dedicate the third day of our Bioplastics Business Breakfast, during the upcoming K’2013 trade fair, to durable applications. Finally this issue is once again rounded off by another of our basics articles, this time on succinic acid, and lots of industry and applications news. As usual, our events calendar provides an overview about forthcoming conferences and trade shows. I’m looking forward to seeing one or more of you at one of these events. Until then, we hope you enjoy reading bioplastics MAGAZINE

Sincerely yours Michael Thielen

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bioplastics MAGAZINE [03/13] Vol. 8

Content

03|2013

Injection Moulding 16 Not only for film making 18 Watch bracelets made in Austria 20 Toys and more... (Cover Story) 21 Pitcher with separate bamboo handle 22 Liquid wood and more …

May/June

Editorial . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3

From Science & Research

News. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 - 8

24 Lacquer from tomato for metal cans 28 Bioplastic products from citrus wastes 36 Advances in PLA chemistry

Events. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9 Cover Story. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20 Application News. . . . . . . . . . . . . . . . . . . . . . . . 34 - 35

Chinaplas Review

Suppliers Guide. . . . . . . . . . . . . . . . . . . . . . . . . 66 - 68

31 Chinaplas

Event Calendar. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69

Materials

Companies in this issue . . . . . . . . . . . . . . . . . . . . . 70

39 Innovative biopolymer blend

Did you know

PLA Recycling

10 Did you know…? …about meat

40 Bioplastics want to be recycled as well 42 PLA recycling via thermal depolymerization 45 Solvent based PLA recycling 46 PLA recycling with degassing 48 Mechanical PLA recycling 49 Supporting ecological advantages 50 Better-than-virgin recycled PLA 52 Chemically recycling post-consumer PLA 54 Recycling ‘hands on‘ 55 Pelletizing and crystallizing of PLA

Report 11 New data on land-use 12 Valorisation of by-products 14 Greenhouse gas-based PHA 58 Bioplastics for food packaging

Portrait 56 10 years FKuR

Opinion 57 Biobased: Lose the hyphen 63 Market studies 64 Reliable and transparent

Basics

Coverphoto: Philipp Thielen Photo page 3: Sven Keitlinghaus

Cover

A part of this print run is mailed to the readers wrapped in Green PE envelopes sponsored by FKuR Kunststoff GmbH and Oerlemans Plastics B.V.

Envelopes

Editorial contributions are always welcome. Please contact the editorial office via mt@bioplasticsmagazine.com.

bioplastics MAGAZINE tries to use British spelling. However, in articles based on information from the USA, American spelling may also be used.

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bioplastics MAGAZINE is read in 91 countries.

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60 Succinic acid

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News

Green materials in rapid prototyping

Cardia and University of Sydney explore PPC applications

In early April of this year, Merseburg University of Applied Sciences joined the Research for the Future stand, run by the Central German Universities at the Hanover Trade Fair, and presented the latest FABIO project results.

Cardia Bioplastics Limited (Mulgrave, Victoria, Australia) recently announced a collaboration of the University of Sydney with CO2 Starch Pty Ltd (100% owned subsidiary of Cardia).

FABIO stands for the FAbrication of parts with BIOplastics and simply means that, in the framework of this project, processes and devices are developed which enable the use of biobased polymers in Rapid Prototyping. The research team and project leader, Dietmar Glatz, presented a rapid prototyping system based on fused layer modelling (FLM). For the very first time, thermo plastic, biobased polymers are processed in granular form using this method. The development of this rapid prototyping system provides a new basis for construction materials and has enormous developmental potential. Since November 2011, functional prototypes have been produced from bioplastics, opening up new fields of application. In the framework of the FABIO project, Merseburg University of Applied Sciences co-operates with four partners from industry, 30 designers and Magdeburg-Stendal University of Applied Sciences. The manufactured prototype is living proof of the usability of bioplastics in technical fields. The Hanover Trade Fair, which took place from April 8 th. - April 12th. is the world’s biggest investment goods trade fair and an important platform for scientific institutions, universities and business developers from all branches of industry. www.hs-merseburg.de

(Photo: HS Merseburg)

Cardia launched the world’s first CO2+Starch biodegradable carrier bag in 2010. This patented breakthrough opened up the potential for biodegradable polymers and polymeric blends for packaging applications to mitigate environmental problems caused by non-degradable polymeric and plastic materials. Cardia advanced its patented CO2+Starch development one step further and produced a biodegradable CO2 + Starch bag with good mechanical properties. CO2 Starch Pty Ltd’s ground breaking work allows polypropylene carbonate (PPC) resins to be blended with starch with the potential to be cost-effectively transformed into a wide variety of industrial products that includes packaging, medical and coatings and engineering polymers. The research agreement also allows for the PPC resin to be used for bio-medical applications such as tissue scaffolds and drug delivery agents. CO2 Starch Pty Ltd Chairman Pat Volpe said: “In collaboration with the University of Sydney, CO2 Starch Pty Ltd is looking to expand its patented PPC+starch blending technology into application within the packaging industry before addressing potential applications in other industries including but not limited to the medical industry.” Volpe said they are working with the University of Sydney to develop and adopt their new unique technique that aims to produce PPC, a biodegradable aliphatic polyester which is synthesized from copolymerization of carbon dioxide (CO2) and propylene oxide (PO). The technique is a one-step manufacturing process (rather than two) that also lowers the levels of residual zinc catalyst and potentially lowers the costs of PPC.” The aim is to apply the technology to many applications and produce alternative renewable biodegradable plastics at an economical price point whilst maintaining good mechanical properties that meet international compostability standards. MT www.cardiabioplastics.com www.sydney.edu.au

bioplastics MAGAZINE [03/13] Vol. 8

News

Sulzer to build high PLA production plant in Asia

Renewable farnesene

Sulzer (Winterthur, Switzerland) has been awarded a contract for the delivery of a production plant based on Sulzer’s proprietary polylactic acid (PLA) technology. The facility with a capacity of more than 10,000 tonnes per year will produce high performance PLA for a broad range of applications. Commercial production is planned to start in the second half of 2014.

Amyris, Inc. (Emeryville, California, USA), a leading renewable chemicals and fuels company, recently announced the first commercial shipment from its new plant in Brazil. Amyris’s first purpose-built industrial fermentation facility produces Biofene®, Amyris’s brand of renewable farnesene, a chemical building block to be used in a range of specialty chemical, fuel and polymer applications.

Both parties have agreed to leverage Sulzer’s technology and pilot facilities to support the customer in the development of innovative solutions for the Asian polymer market. Sulzer’s proprietary technology allows the continuous production of high-performance PLA grades with very low residual monomer levels and a wide possible viscosity range. The new PLA produced with Sulzer technology exhibits an excellent crystallinity and withstands temperatures up to 180°C (HDT-B for stereocomplex PLA). Applications in the automotive, electronics and the textile industry based on this new type of material are currently under development and will see their market appearance in the near future. In order to further facilitate the PLA market development and to emphasize its commitment to the biopolymer industry, Sulzer has recently startedup its own PLA pilot plant for 1,000 tonnes per year in Switzerland. MT www.sulzer.com

With its unique chemical structure, Biofene is ideally suited for various polymer applications. Amyris is currently collaborating with two of its partners to incorporate Biofene in breakthrough applications. Amyris is working with Japan’s Kuraray to use Biofene to replace petroleum-derived feedstock in the production of specified classes of high-performing polymers for the tire industry. Initial testing indicates that Biofene provides differentiated performance for rubber tires by reducing rolling resistance, which improves fuel economy, without reduction in tire wear. Amyris has partnered with Italy’s Gruppo M&G to incorporate Biofene as an ingredient in PET (polyethylene terephthalate) resins for packaging applications. While lightweight, shatterproof and recyclable, plastic bottles are not very good at keeping air from reaching its contents, particularly food products. When processed, Biofene helps form an oxygen barrier for plastic bottles and jars. Amyris’s Biofene plant in Brotas, in the state of São Paulo, Brazil, sources its sugarcane feedstock locally from the Paraíso mill. Prior to the start-up of this facility, Amyris relied solely on contract manufacturing for commercial production. www.amyris.com

Significantly enhanced heat and impact resistance Teijin Limited Tokyo, Japan, recently announced that it has developed technology to significantly enhance the heat and impact resistance of PLANEXT, the company’s highperformance bio-polycarbonate. The technology modifies the molecular design of Planext to achieve greatly improved heat resistance with a glasstransition temperature of 120°C, as well as superior resistance to impact. In addition, a separate proprietary flame-retardant technology enables Planext to achieve toplevel flame retardancy of UL94V-0 at 1.6mm. Teijin will develop markets for Planext as a strategic bio- and next-generation transparent material with new applications in the electronics, architecture and exterior fields, starting with the Japanese market. Annual production capacity at the

bioplastics MAGAZINE [03/13] Vol. 8

company’s Matsuyama Factory in Ehime Prefecture, Japan is expected to expand to 3,000 tons within a few years. Planext is an eco-friendly bio-polycarbonate made with bio-content based on isosorbide from corn-starch and other plants. In addition to excellent moldability and durability, it is superior to oil-derived polycarbonates in terms of surface hardness (pencil hardness rank: H), weather and chemical resistance, and light transmission of 92%. With its newly enhanced heat and impact resistance, Planext is now a material suited for a much wider range of applications than ever before. MT www.teijin.com

News

Purac and Rotec cooperate in Russia

Million-invest in bioplastic production

In early April CJSC Rotec (Moscow, Russia, a subsidiary of the Renova Group of companies) and Purac (Gorinchem, The Netherlands), a subsidiary of CSM), signed an agreement on the development of a project to create a unique in the world high-tech biopolymer production facility in Russia.

The Russian company PoliKompleks plans to build a complex for rectification of lactic acid and for the production of bioplastics in the Kaliningrad region.

The agreement envisages analysis of opportunities to set in Russia a 100,000 tonnes/annum facility that will produce PLA polymers for subsequent production of biodegradable plastics. A facility of this scale operating on the basis of Purac’ technology of industrial PLA and lactides production from renewable resources from locally available biomass, and their polymerization knowhow, will be the first production chain of its kind in Europe. In the study, Rotec will focus on a location analysis related to the availability of optimal agricultural land and feedstocks and potential production locations, as well as research of the Russian market. Purac, leading player in natural food preservation and biobased building blocks & chemicals, will focus on the analysis of the optimal available feedstock-to-PLA technologies and defining the business case. In the event of positive project feasibility testing, the new facility will allow for industrial production of a revolutionary generation of polymers that will be unique for Russia and globally. According to Renova’s estimate, project investments will exceed rubles (RUB) 16bn (€ 400mio). As Renova Group’s High-Tech Asset Development Director Mikhail Lifschitz says, ”the prospect of creating a production facility of this kind will not only contribute to improvement of overall environmental situation in our country and the development of agricultural sector as the core supplier of raw materials for production of biopolymers, but will also improve the image of Russian economy as the user of environmentally friendly newest-generation materials”.

The administration of the Kaliningrad region informed in a press release that an agreement was signed at the recent Hanover Fair (Hanover, Germany). According to that press release, the plants will produce about 50,000 tonnes/annum of bioplastics as well as about 12,000 tonnes/annum of biodegradable thawing agents on the basis of lactic acid or of polylactides (PLA) with a targeted turnover of 1.4 billion rubles (RUB) (€ 35 million) per year. The completion of the complex is scheduled for 2016, work to be started this year. The investment volume amounts to approximately RUB 1.2 bn (€ 30 million). A precise location of the facilities was not disclosed in the press release. The project will be the basis of a biochemical cluster. Together with similar industrial projects, e.g. for the automotive and shipbuilding industries, it will become a focus for future economic growth in the region. The whole project is part of a development plan of the bio-economy in Russia, known as Bio-2030. The strategic goal is to increase the bio-economy to 1% of the GDP by 2020 and 3% by 2030. For the Russian government bio-economy is an important part of the modernization of the economy, creating social benefits and new jobs, and working against depopulation in the rural areas. The company PoliKompleks has been active in the field of industrial biotechnology in several Russian regions as well as in Kazakhstan and Venezuela since 2009. According to the information from the Kaliningrad administration PoliKompleks cooperates (among others) with the Dresden, Germany based company Sarad. MT Source: www.nov-ost.info

Renova is also the major shareholder of the Swiss corporations Sulzer and Oerlikon. MT www.purac.com www.renova.ru

bioplastics MAGAZINE [03/13] Vol. 8

News

15% annual growth for biodegradable plastics According to a new IHS Chemical global market research report, mounting consumer pressure and legislation such as plastic bag bans and global warming initiatives will increase demand for biodegradable plastics. In North America, Europe and Asia demand will rise to nearly 525,000 tonnes in 2017 (from 269,000 tonnes in 2012). This represents an average annual growth rate of nearly 15% during his period. The IHS Chemical CEH Biodegradable Polymers Marketing Research Report focuses on biodegradable polymers, including compostable materials, but not necessarily including all biobased products. In terms of biodegradable polymer end-uses, IHS estimate that the food packaging (including fast-food and beverage containers), dishes and cutlery markets are the largest enduses and the major growth drivers. In both North America and Europe, these markets account for the largest uses and strong, double-digit growth is expected in the next several years. Foam packaging once dominated the market and continues to represent significant market share for biodegradable polymers, behind food packaging, dishes and cutlery. Compostable bags, as well as single-use carrier plastic bags, follow foam packaging in terms of volume. “The biodegradable polymers market is still young and very small, but the numbers are off the charts in terms of expected demand growth and potential for these materials in the coming years,” said Michael Malveda, principal analyst of specialty chemicals at IHS Chemical and the report’s lead author. “Food packaging, dishes and cutlery constitute a major market for the

product because these materials can be composted with the food waste without sorting, which is a huge benefit to the waste management effort and to reducing food waste and packaging disposal in landfills. Increasing legislation and consumer pressures are also encouraging retailers and manufacturers to seek out these biodegradable products and materials.” In 2012, Europe was the dominant market for biodegradable polymers consuming 147,000 tonnes or about 55% of world consumption; North America accounted for 29% and Asia approximately 16%. Landfill waste disposal and stringent legislation are key market drivers in Europe and include a packaging waste directive to set recovering and recycling targets, a number of plastic bag bans, and other collection and waste disposal laws to avoid landfill. The most acceptable disposal method for biodegradable polymers - according to IHS - is composting. However, composting requires an infrastructure, including collection systems and composting facilities. Composting has been a growing component of most European countries’ municipal solid waste management strategies for some time, and the continent has an established and growing network of facilities, while the U.S. network of composting facilities is smaller, but expanding. In 2012, the two most important commercial, biodegradable polymers were polylactic acid (PLA) and starch-based polymers, accounting for about 47% and 41%, respectively, of total biodegradable polymers consumption. MT www.ihs.com

Biome Bioplastics to investigate lignin The UK’s innovation agency, the Technology Strategy Board, has awarded a £150,000 (€ 176,000) grant to a consortium led by Biome Technologies, to investigate a biobased alternative for the oil derived organic chemicals used in the manufacturer of bioplastics.

process to determine whether aromatic chemicals can be isolated from the lignin in significant quantities. These aromatic chemicals are to replace the oil-derived equivalent currently used in the production of a polyester that conveys strength and flexibility in some of BIOME’s bioplastics.

The research will be undertaken by the group’s bioplastic division Biome Bioplastics (Southampton, UK) in conjunction with the University of Warwick’s Centre for Biotechnology and Biorefining. The project is scheduled to last nine months and is about scaling up laboratory results to test their technical feasibility for commercial use, as reported by packagingeurope.com.

“The environmental and social concerns surrounding the use of fossil fuels make lignin a compelling target as a source of chemicals”, explains Professor Tim Bugg, Director of the Centre. “Often considered a waste product, it may provide a sustainable source of building blocks for aromatic chemicals that can be used in bioplastics”.

One of the most interesting sources of biobased chemicals is lignin, a waste product of the pulp and paper industry, thus being a potentially abundant feedstock that could provide the foundation for a new generation of bioplastics. Biome has partnered with the University of Warwick’s Centre for Biotechnology and Biorefining that is pioneering academic research into lignin degrading bacteria. Together they want to develop methods to control the lignin breakdown

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“The bioplastics market remains small compared to that of fossil-based polymers”, comments Biome Bioplastics CEO Paul Mines. “Growth is restricted by the price of bioplastic resins being 2-4 times that of their petrochemical counterparts. We anticipate that the availability of a high performance polymer, manufactured economically from renewable sources would considerably increase the market”. MT www.biomebioplastics.com

Events

International conference in Cologne With 180 participants (60% up on 2012) from 23 countries (up 50%), this year’s International Conference on Industrial Biotechnology and Bio-based Plastics & Composites organized by the nova-Institute (Hürth, Germany) further established itself as a major industry meeting-place and visitors both grew in number and became more international. Lengthening the conference to three days to provide comprehensive coverage of political, industrial and scientific issues proved a success. The focus of this year’s conference was on the United States and Germany. The large number of American speakers and participants contributed to a thrilling dialogue between the world’s two leading industrial biotechnology countries.

Policy

Biomaterial of the Year 2013 There was great interest in the awards ceremony for the Innovation Prize for Biomaterial of the Year 2013, which, as in previous years, was sponsored by Coperion GmbH and, for the fifth time, conference participants voted for the winners. This prize is awarded to new practical applications of biobased materials. Around 20 companies from the USA and Germany entered the competition.

Industry

The First prize, Biomaterial of the Year 2013, was awarded to Newlight Technologies, LLC for its Airflex™ (AirCarbon™) resins. CEO Mark Herrema presented a new kind of highyield technology chain to produce thermoplastics (PHAs) from greenhouse gases (such as CO2 and methane). See page 14 for a more comprehensive article on this technology

During the industry sessions on the first and second day, companies such as Clariant Produkte (Germany), BASF (Germany), DuPont (USA), Bayer MaterialScience (Germany), NatureWorks (USA), Johann Borgers (Germany) and FlexForm Technologies (USA) presented their plans for biorefineries, new biobased polymers and natural-fibrereinforced composites.

The 2nd prize went to fischerwerke GmbH & Co. KG (Germany) for their bio-PA universal UX green plug and the 3rd prize was awarded to 4e solutions GmbH & TECNARO GmbH (Germany) - ajaa! For their product line of sustainable household articles from bioplastics - made in Germany. Both were already introduced in earlier issues of bioplastics MAGZINE. MT

The first day was largely devoted to discussing the political framework that could drive the development of the biobased economy and, above all, biobased materials and products.

Science This was the first time that the conference had been extended to a third, scientific day, which nova-Institute organised with the collaboration of Professor Dr Jörg Müssig from Bremen University of Applied Science’s Bionics Innovation Centre. The organisers had succeeded in bringing together 13 renowned speakers from the USA and Germany.

www.biowerkstoff-kongress.de www.nova-institut.eu

left to right: Uta Kühnen (Coperion, Mark Herrema, Newlight, Michael Carus, nova-Institute)

bioplastics MAGAZINE [03/13] Vol. 8

Did you know

Did you know…?

nova-Institute

kg meat per capita and year

…about meat

Huerth, Germany

he per capita meat consumption in the USA amounted to about 108 kg per year in 2012 [1]. The projection of FAPRI [1] until 2025 is that this level of consumption will rise only slightly to about 109 kg/year. This meat consumption level, one of the highest in the world, can be regarded as a kind of saturation level.

140.0 120.0 100.0 80.0 60.0 40.0 20.0 0.0

2000 2003 2006 2009 2012 2015 2018 2021 2024 USA China Indiana

Fig. 1: Per capita meat consumption in the USA, India and China (Source [1])

m2/kg

50 40 30 20 10 0 Beef 34,5 (28-50)

Pork 11 (9-13)

Chicken 9 (8-10)

Fig. 2: Land use for livestock products (in m2/kg of product) (Source [2, 3])

e or n!

t m ke a E ic

(image: iStock: Chris3fer)

by Stephan Piotrowski

bioplastics MAGAZINE [03/13] Vol. 8

Wheat 1,5

If this consumption level would prevail in the whole world, this would equate to about 720 million tonnes of meat per year today (6.7 billion people) or about 1 billion tonnes in 2050 (given the UN population projection of 9.3 billion people by 2050). Currently, global meat consumption amounts to about 270 million tonnes, so that consumption would rise by almost 3 times today or almost 4 times by 2050. The current meat consumption demands about 60% of harvested agricultural biomass worldwide as feed. Assuming that this level of feed use is already the limit today, taking into account the already high competition for other biomass uses, mankind would therefore need today almost 2 more planets to satisfy the world’s appetite for meat. In addition to the total meat consumption, the kind of meat also plays an important role on the required land. Beef for example requires about twice as much land as pork or chicken. Looking out into 2050, approximately 40% yield increases are projected by the FAO for most arable crops. Ignoring all other influencing factors, two more planets may therefore still suffice to provide enough meat to the world. However, this calculation disregards, among many more, one important aspect: The increasing demand for food, energy and materials not only due to a growing world population, but also per person due to economic development and higher living standards. [1] Food and Agricultural Policy Research Institute (FAPRI) 2012 [2] M. de Vries, I.J.M. de Boer; Comparing environmental impacts for livestock products: A review of life cycle assessments; Livestock Science 128 (2010) 1–11; Elsevier [3] Jørgen E. Olesen: Scenarios of land use in Denmark under climate change, Aarhus University, Denmark; bit.ly/17oWTa0

Report

New data on land-use Feedstock required for bioplastics production accounts for only a minimal fraction of global agricultural area.

In a world of fast growing population with an increasing demand for food and feed, the use of feedstock for non-food purposes is often debated controversially. The new brochure Bioplastics - facts and figures recently published by European Bioplastics, moves the discussion on to a factual level. Of the 13.4 billion hectares of global land surface, around 37% (5 billion hectares) are currently used for agriculture. This includes pastures (70%, approximately 3.5 billion hectares) and arable land (30%, approximately 1.4 billion hectare). These 30% of arable land are further divided into areas predominantly used to grow crops for food and feed (27%, approximately 1.29 billion hectares), as well as crops for materials (2%, approximately 100 million hectares, including the share used for bioplastics), and crops for biofuels (1%, approximately 55 million hectares).

Minimal fraction of land used for bioplastics European Bioplastics market data depicts production capacities of around 1.2 million tonnes in 2011. This translates to approximately 300,000 hectares of land-use to grow feedstock for bioplastics. In relation to the global agricultural area of 5 billion hectares, bioplastics make use of only 0.006 %. Metaphorically speaking, this ratio correlates to the size of an average cherry tomato placed next to the Eiffel Tower.

No competition to food and feed A glance at the global agricultural area and the way it is used makes it abundantly clear: 0.006 % used to grow feedstock for bioplastics are nowhere near being in competition with the 98 % used for pastures and to grow food and feed. According to European Bioplastics, increasing the efficiency of feedstock and agricultural technology will be key to assuring the balance between land-use for innovative bioplastics and land for food and feed. The emergence of reliable and independent sustainability assessment schemes will also contribute to this goal. www.european-bioplastics.com

Source: European Bioplastics | Institute for Bioplastics and Biocomposites (October 2012) / FAO

he surface required to grow sufficient feedstock for todayâ&#x20AC;&#x2122;s bioplastic production is less than 0.006 % of the global agricultural area of 5 billion hectares. This is the key finding published recently by European Bioplastics, based on figures from the Food and Agriculture Organization of the United Nations (FAO) and calculations of the Institute for Bioplastics and Biocomposites (IfBB, University of Applied Sciences and Arts, Hanover, Germany).

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Report

Valorisation of by-products BioTRANSformation of by-products from fruit and vegetable processing industry into valuable BIOproducts by Thomas Dietrich TRANSBIO Coordinator TECNALIA Miñano – Álava, Spain

ustainable use of renewable raw materials is required to become a long lasting biobased economy. OECD stated already in 2001 that the use of eco-efficient bio-processes and renewable raw materials is one of the key strategic challenges for the 21st century. Nevertheless, renewable raw materials must be used in a sustainable and environmental sound manner, as increasing demand for industrial products and energy from biomass will inevitably lead to an expansion of global arable land at the expense of natural ecosystems. Current strategies for utilization of biomass for food, biofuels and biomaterials resulted in some areas in increased land utilization for monocultures and competition of raw materials for food and fuel. According to OECD-FAO Agricultural Outlook (2012), some of 65% of EU vegetable oil, 50% of Brazilian sugarcane and 40% of US corn production are being used as feedstock for biofuel production. In parallel worldwide available agricultural area per person reduced significantly from 1,05 ha (1980) to 0,70 ha (2011) (FAOSTAT, 2013). Therefore, new untapped renewable resources such as by-products from fruit and vegetable transforming industry must be evaluated for their potential to be used as base material for biomaterials and platform chemicals. The aim of the European project TRANSBIO (grant agreement no. 289603) is the implementation of an innovative cascading concept for the valorisation of by-products from fruit and vegetable processing industry, using environmental friendly biotechnological solutions to transform these by-products into biopolymers, platform chemicals and enzymes. Currently, Transbio is characterizing several fruit and vegetable by-products in order to select the most appropriate ones for further pre-treatment and enzymatic hydrolysis. In order to obtain a broad application potential for the by-products selected, the partners investigate different fermentation strategies – submerged cultivation in liquid media (bacteria, yeasts) and solid state fermentation (fungi). Parallel to on-going by-product characterisation and selection, partners identify several new strains to be utilized in the concept. Beside optimisation and up-scaling of fermentation protocols, down-stream processing will be developed keeping in mind economical feasible and sustainable procedures. The procedures will be implemented for extra cellular succinic acid production using novel non-conventional yeast strains, extracellular enzyme formation in solid state fermentation, as well as polyhydroxybutyrate (PHB) production in submerged fermentation. The obtained PHB will be tested in packaging application, enzymes will be proved for detergent utilisation and succinic acid will be purified for food applications. In order to achieve these objectives, the project is receiving funding from the European Union’s Seventh Framework Programme (FP7/2007-2013). www.transbio.eu

bioplastics MAGAZINE [03/13] Vol. 8

Market study on Bio-based Polymers in the World

Capacities, Production and Applications: Status Quo and Trends towards 2020 Bio-based polymers – Production capacity will triple from 3.5 million tonnes in 2011 to nearly 12 million tonnes in 2020 Germany’s nova-Institute is publishing the most comprehensive market study of bio-based polymers ever made. The nova-Institute carried out this study in collaboration with renowned international experts from the field of bio-based polymers. It is the first time that a study has looked at every kind of biobased polymer produced by 247 companies at 363 locations around the world and it examines in detail 114 companies in 135 locations (see table). Considerably higher production capacity was found than in previous studies. The 3.5 million tonnes represent a share of 1.5 % of an overall construction polymer production of 235 million tonnes in 2011. Current producers of bio-based polymers estimate that production capacity will reach nearly 12 million tonnes by 2020.

million t/a

Bio-based polymers: Evolution of production capacities from 2011 to 2020

2011

2012

PLA

2013

2014

Starch Blends Polyolefins

PET

2015

2016

2017

PHA

2018

2019

2020

PBAT

Content of the full report This over 360-page report presents the findings of nova-Institute’s year-long market study, which is made up of three parts: “market data”, “trend reports” and “company profiles”. The “market data” section presents market data about total production and capacities and the main application fields for selected bio-based polymers worldwide (status quo in 2011, trends and investments towards 2020). The “trend reports” section contains a total of six independent articles by leading experts in the field of bio-based polymers and plastics. Dirk Carrez (Clever Consult) and Michael Carus (nova-Institute) focus on policies that impact on the bio-based economy. Jan Ravenstijn analyses the main market, technology and environmental trends for bio-based polymers and their precursors worldwide. Wolfgang Baltus (NIA) reviews Asian markets for bio-based resins. Roland Essel (nova-Institute) provides an environmental evaluation of bio-based polymers, and Janpeter Beckmann (novaInstitute) presents the findings of a survey concerning Green Premium within the value chain leading from chemicals to bio-based plastics. Finally, Harald Kaeb (narocon) reports detailed information about brand strategies and customer views within the bio-based polymers and plastics industry. These trend reports cover in detail every recent issue in the worldwide bio-based polymer market. The final “company profiles” section includes 114 company profiles with specific data including locations, bio-based polymers, feedstocks, production capacities and applications. A company index by polymers, and list of acronyms follow.

PBS

-Institut.eu | 2013

Evolution of the shares of bio-based production capacities in different regions 2011

20%

2020

15%

14% 13%

North America

-Institut.eu | 2013

13% 18%

52%

55%

South America

To conduct this study nova-Institute developed the “Bio-based Polymers Producer Database”, which includes a company profile of every company involved in the production of bio-based polymers and their precursors. This encompasses (state of affairs in 2011 and forecasts for 2020) basic information on the company (joint ventures, partnerships, technology and bio-based products) and its various manufacturing facilities. For each bio-based product, the database provides information about production and capacities, feedstocks, main application fields, market prices and biobased share. Access to the database is already available. The database will be constantly updated by the experts who have contributed to this report. Buyers of the report will have free access to the database for one year. Everyone who has access to the database can automatically generate graphics and tables concerning production capacity, production and application sectors for all bio-based polymers based on the latest data collection.

Order the full report The full 360-page report contains three main parts – “market data”, six “trend reports” and 114 “company profiles” – and can be ordered for 6,500 € plus VAT at: www.bio-based.eu/market_study This also includes oneyear access to the “Biobased Polymers Producer Database”, which will be continuously updated.

Thermosets

BIO-BASED POLYMERS ©

“Bio-based Polymers Producer Database” and updates to the report

Asia

Europe

Quellen: FEDIOL 2010

AVERAGE BIOMASS CONTENT OF POLYMER

Cellulose Acetate CA 50% Polyamide PA rising to 60%* Polybutylene Adipate PBAT rising to 50%* Terephthalat Polybutylene Succinate PBS rising to 80%* Polyethylene PE 100% Polyethylene Terephthalat PET 30% to 35%*** Polyhydroxy Alkanoates PHAs 100% Polylactic Acid PLA 100% Polypropylene PP 100% Polyvinyl Chloride PVC 43% Polyurethane PUR 30% Starch Blends **** 40% Total companies covered with detailed information in this report Additional companies included in the “Bio-based Polymer Producer Database” Total companies and locations recorded in the market study * ** *** ****

PRODUCING COMPANIESUNTIL 2020

LOCATIONS 9 14 3

15 17 3

11 3** 4 14 27 1 2 10 19 114 133 247

12 2 4 16 32 1 2 10 21 135 228 363

Currently still mostly fossil-based with existing drop-in solutions and a steady upward trend of the average bio-based share up to given percentage in 2020 Including Joint Venture of two companies sharing one location, counting as two Upcoming capacities of bio-pTA (purified Terephthalic Acid) are calculated to increase the average bio-based share, not the total bio-PET capacity Starch in plastic compound

Report

Greenhouse gas-based PHA A Breakthrough In Yield, A New Paradigm in Carbon Capture by Karen Laird

hen Mark Herrema and Kenton Kimmel set out in 2003 to develop a technology to convert greenhouse emissions into useful materials, they were armed with optimism, idealism, a healthy measure of self-confidence and the resolution to succeed. Today, ten years, ten patents and millions of dollars in research and development later, they’re the founding partners of Newlight Technologies LLC, a company specialized in high yield greenhouse gasto-PHA conversion and functionalization technologies, that is fast overturning all preconceptions about biopolymers. “When we started, our goal, simply put, was to reverse climate change by using carbon emissions to produce materials on a global scale,” says Mark Herrema. “Not only were we seeking a way to turn carbon emissions into plastics that actually removed more carbon from the air than they produced, we also knew that the only way we could do this on a commodity scale was if our material could out-compete on its own merits, without reference to environmental benefit.” In other words, the plastic materials Newlight produced would need to match oil-based plastics on performance and out-compete on price, definitely not features that had characterized most bioplastics up until now.

Technological hurdles Kimmel and Herrema soon discovered that the idea of converting carbon-containing gases into plastics - in this case, PHA bioplastic - was not a new one; indeed, it was an ongoing object of study at companies in countries around the world, from Germany to the US to China. Everywhere, however, everyone kept running up against the same, seemingly insurmountable hurdle: yield. All currently available technologies had thus far failed to deliver a cost-effective and economically viable process

bioplastics MAGAZINE [03/13] Vol. 8

Report

to produce greenhouse gas-based PHA plastic at scale. “Obviously, more expensive PHA wasn’t something that could move at meaningful scale on the market,” said Herrema. “In addition, we found that the performance of the PHAs produced via the greenhouse gas route needed to be significantly improved to render these functionally competitive with oilbased plastics.” Next to these yield and performance limitations, Newlight also encountered new challenges, such as gas mass transfer conversion efficiency—that is, the amount of energy required to make greenhouse gases chemically accessible. Herrema: “Basically we realized that we were facing the task of having to develop new technology, which meant generating novel methods to approach yield, performance, and mass transfer efficiencies, and capabilities in catalyst engineering, reactor design, and polymer performance.”

Breakthrough “It took years, and it was far from easy”, said Mark Herrema. “But we finally cracked it.” The central problem, as Newlight had discovered in the course of its work, was the fact that the company’s proprietary biocatalyst, developed to convert air and greenhouse gasses, such as methane and carbon dioxide into PHA, was controlled by a negative feedback control loop. This meant that when the concentration of plastic produced reached a certain maximum level, it would stop making plastic. To address this, Newlight developed a set of novel catalyst engineering tools, aimed at producing a biocatalyst with a malleable overproduction control switch—that is, the ability to turn off this negative feedback response. By turning off this response, the catalyst would overproduce PHA, thereby fundamentally altering the yield profile of the process. “That, at least, was the theory,” said Herrema. “Getting it to work in practice was trickier. “ Yet ultimately, work it did, and with dramatic results, as illustrated by the immediate 500% increase in yield performance compared to before. The net result was that Newlight had successfully developed a market-driven solution to capturing carbon: technology able to produce plastic from greenhouse gas for significantly less than the cost to produce plastic from oil. In short, a PHA plastic offering a revolutionary value proposition. Herrema: “Explaining it like this makes it sound so simple. But an incredible amount of time and R&D ten years and millions of dollars - went into this development, and it unlocked something tremendous.“

At the same time, Newlight also developed a suite of polymer functionalization tools, and teamed with key partners to improve the performance of its resins, addressing classical PHA functional challenges, such as strength, flexibility, thermal stability, molecular weight, and aging. As a result, the company was able to develop the ability to tailor its materials to meet a wide range of performance specifications, spanning replacements for various grades of polypropylene, polyethylene, ABS, and TPU, in both durable and biodegradable grades.

New challenges: sales and capacity expansion In 2012, Newlight began selling its Airflex (also known as AirCarbon) plastics for the first time. Since the commencement of sales, demand for Newlight’s materials has grown significantly in excess of capacity, with over 5,700 tonnes of material now under executed letter of intent for purchase. “The response of the market has been overwhelming - we’ve been inundated with applications. In fact, everything we make is presold,” said Herrema. Moreover, in recognition of the company‘s technological and commercialization achievements in 2012, Newlight‘s plastic was named “2013 Biomaterial of the Year“ by the novaInstitut at an international biomaterials conference in April 2013 (see p.9). Newlight’s customers and product development partners already include some of the largest manufacturers in the world, including Fortune 500 companies, brand-name market leaders, and an $8 billion consumer goods manufacturing company—making everything from chairs and containers to caps and bags. “We’re getting ready for a number of product launches,” said Herrema. “We’re preparing to launch a furniture line in the course of this year.” The company’s new focus is on growth and expansion, in order to be able to keep up with demand and, ultimately, to accomplish its founding objective: to use its carbon-negative plastics as a market-driven tool to reverse climate change. Newlight has its eye on a number of sites for a facility with a multi-thousand tonne per year projected annual capacity of. A first step in this direction is the capacity expansion that Newlight will have in place by the end of this year. “We’ve got the technology,” said Herrema. “The next challenge is to get it out to the market at large scale. That’s our mission now.” www.newlight.com

The breakthrough had immediate and profound impact. “We were able to reduce our unit operations by a factor of 3, the company’s capital equipment cost dropped by a factor of 5, and total operating costs were dramatically reduced.”

bioplastics MAGAZINE [03/13] Vol. 8

Injection Moulding

Not only for film making

Potential applications: ecovio IS for injection moulding

ix years ago BASF launched the compostable plastic ecovio® – which is biodegradable as defined by EN 13432 and based to a large extent on renewable resources. Since then the material was able to prove itself in a variety of film applications. To date, the primary fields of application have been bags for collecting biodegradable waste and mulching film, which helps to cultivate fruit and vegetables in fields. Now BASF has once again added variants to its range of the compostable and partially biobased plastic ecovio. The ecovio T2308 is now available for the processing method of thermoforming. For injection moulding the company offers the new ecovio IS1335 grade. Both of these products are now available in commercial quantities. They consist predominantly of renewable raw materials and lend themselves well for being dyed.

Thermoforming: Processing on conventional flat-film installations The new ecovio T2308 can now be used to make thermoformed trays and cups can. It exhibits mechanical properties similar to those of amorphous PET, but it differs from this conventional thermoforming material by its compostability and its high content of renewable resources (PLA). The content of ecoflex®, which is BASF’s compostable polyester, accounts for the fact that the material is not too stiff or too brittle. Thus, thermoformed trays and cups are not damaged during transportation and storage. The ecoflex component also ensures a balanced stiffness-to-strength ratio and sufficient low-temperature impact strength. The processing window for ecovio T, between 80°C and 120°C, is very broad in comparison to other plastics. Processing can be carried out on conventional flat-film

bioplastics MAGAZINE [03/13] Vol. 8

installations and at the processing speeds that are typical for thermoforming. Like all ecovio grades, it also complies with the stipulations for products that come into contact with food. The material is translucent and can be adequately sealed with cover films.

Injection molding: For thin-walled highquality packaging The second novelty in the ecovio product line, the injectionmoulding grade ecovio IS1335, can be processed using single-cavity or multi-cavity moulds that are equipped with or without hot runners. This material exhibits moderate flowing characteristics and is dimensionally stable under heat up to 55°C (HDT-B). This variant lends itself for thin-walled, complex and high-quality packaging, which should preferably be manufactured by injection moulding and should be compostable. The product can also be decorated employing in-mould labeling. Results of experiments on compostability show that, depending on the application, injection-moulded products made of ecovio IS1335 having wall thicknesses of as much as 1.1 mm degrade in accordance with the EN 13432 standard for compostable packaging. Thicker mouldings will certainly biodegrade completely too, however, it takes longer than required in the compostability standards. A first serial application of this new injection mouldable ecovio grade is just being finalized together with a customer, a newcomer in the market. In this application (for the time being still confidential) the compostable plastic is part of a system solution for food packaging. The injection moulded grade is being used in combination with an ecovio-based multi-layer system with specific barrier properties. www.ecovio.de

organized by

supported by

17. - 19.10.2013

Bioplastics in Packaging

Messe Düsseldorf, Germany

Bioplastics Business Breakfast

Call for Papers now open www.bioplastics-breakfast.com Contact: Dr. Michael Thielen (info@bioplastics-magazine.com)

Bio meets plastics. The specialists in plastic recycling systems. An outstanding technology for recycling both bioplastics and conventional polymers

PLA, an Innovative Bioplastic Bioplastics in Durable applications Subject to changes At the World’s biggest trade show on plastics and rubber: K’2013 in Düsseldorf bioplastics will certainly play an important role again. On three days during the show from Oct 17 - 19, 2013 (!) biopolastics MAGAZINE will host a Bioplastics Business Breakfast: From 8 am to 12 noon the delegates get the chance to listen and discuss highclass presentations and benefit from a unique networking opportunity. The trade fair opens at 10 am.

Injection Moulding

Watch bracelets made in Austria Cooperation agreement for biopolymer use

n April 2012 an extensive research agreement with the Austrian FFG (a governmnet research body) and the Austrian states of Lower Austria and Carinthia was initiated. Cooperation with the Hirsch watch bracelet manufacturers (Carinthia), NaKu (Lower Austria) and Doraplast (Lower Austria) led to an optimisation of bioplastic technology. The first project, the development of an innovative watch bracelet, mount and fixture, made of biologically, compostable and heat resistant bioplastics, will enter the market in the summer of 2013. The commercially available bioplastics did not meet the basic requirements of the project, so the team had to start right from the beginning with the development of a new material. The company NaKu (short for Natürlicher Kunststoff, i.e. natural plastic) is one of Austria’s pioneers in the field of bioplastics. Its range reaches from special compounds, acquired for higher temperatures, or made of waste materials such as sunflower seed cases, through to product development of items for retail sales or industry. Also NaKu supports its clients with the introduction of the process in the market, which is especially complex in the bioplastic sector. In Austria, NaKu supplies (amongst others) retailer Rewe with special fresh storage bags made of bioplastics. An expansion of the product range into kitchen articles led to shared interests with the company Doraplast. “The NaKu company was recommended to us by one of our long term clients, namely the Hirsch company”, said Franz Sprengnagel, manager of Doraplast. “We already had a wide product range of kitchenware made of traditional plastics. An expansion into the bioplastic sector with the company NaKu was perfectly obvious for us.” As a result, the Biodora or NaKuWare product line emerged. During the process of selecting basic working materials, the maximization of renewable and ecological resources was a crucial factor. Another important factor was the high biocompatibility and therefore the tolerance of lactic acid with the human body. The compostability of our kitchenware was not a real factor. In this way, a kitchen product line with 52 parts was generated, and one which is being extended permanently. The main focus for the kitchen line is the contact between food and plastic. This successful cooperation between the companies NaKu and Doraplast was one of the main reasons for the company Hirsch to start an alliance for their high quality watch bracelets. The first step was the invention of a laser-resistant watch bracelet mount made of bioplastics.

bioplastics MAGAZINE [03/13] Vol. 8

The world market leader Hirscharmbänder GmbH, with head office in Klagenfurt, is confident that the issue of sustainability has to be actively faced and expanded in different areas during the production process of high quality watch bracelets. Hirsch is known for its pioneering role when it comes to the development of innovative materials, innovative products or innovative sales programmes. Thus they succeeded again and again in obtaining a clear advantage in the sector, true to the slogan “there is nothing that cannot be improved”. The watch bracelet mount, the so called Hirsch Point, is now produced by ABS/PC in the Far East. “The difficulties were, in particular, to combine the different technologies like thin walls for deep flow processes, laser markability and embossed sheet, with natural polymers. There is almost no experience to draw on,” said Johann Zimmermann, manager of company NaKu said.

g n i D l i Bu D e s a B a Bio futuRe Pe o R u e R fo

At the same time, the production costs had to be reduced while moving production to Europe - a task that is only possible by using a high level of automation. Many principles had to be reviewed and a high number of material tests had to be carried out. The watch bracelet mount will be entering the market in the summer of 2013. The fascinating idea of the NaKu-Doraplast-Hirsch Cooperation is the investigation and introduction of a product line that is sustainable at all levels. The actual successes has convinced all project partners that the Hirsch bracelet mount will not be the last mutual project. More products are already in progress. MT www.naku.at www.hirschag.com www.doraplast.at

Laser markability

Register now! 10 / 11 December 2013 InterContinental Berlin More information is available at: conference@european-bioplastics.org Phone: +49 (0)30 28 48 23 50

www.conference.european-bioplastics.org bioplastics MAGAZINE [03/13] Vol. 8

Cover Story

Toys and more…

arkus Swoboda, founder and managing director of the company BioFactur GmbH (Datteln, Germany) produces small things from bioplastics for day to day life. However, the way to market his products was not always easy.

More than ten years ago he had the idea of making products from bioplastics because he was convinced that petroleum would, sooner or later, no longer be available - or affordable as a resource for plastics. “One day we will ask ourselves, why we didn’t start to do this earlier,” Markus Swoboda said to bioplastics MAGAZINE. Fossil-based plastics, with all the additives and plasticizers, had given him cause for concern, and he initially looked into toys. However, “to replace a conventional plastic material by a renewably sourced one was a tough road to follow - with many drawbacks”. Ten years ago there were not so many different biobased plastics available, he explained. At the end of 2009 Swoboda finally founded BioFactur with some of his first marketable products. Today BioFactur produces sand-box toys and food contact articles such as jugs for juices, drinking cups, lunch boxes or salad servers, exclusively from a cellulose acetacte-based bioplastic with properties in some ways even better than those of tradtional plastics, as Markus Swoboda explained. About 10 tonnes of this material per year is being purchased from a German supplier. “The wood cellulose all comes from sustainably managed forests - 80% from Europe and the rest from Canada,” Markus Swoboda pointed out. For the manufacture of his products he relies on standard injection moulding machines. The processing parameters, such as pressures, temperatures and processing times, do however

bioplastics MAGAZINE [03/13] Vol. 8

have to be adjusted according to the requirements of the resins. Also the moulds have to be designed slightly differently. “A lot of things we had to learn the hard way,” he said. The material is free of any kind of toxic substances such as plasticizers, as confirmed by TÜV Rheinland, an independent testing and certification body. “So no problem for parents to let their kids chew on the toys,” as Swoboda commented. The latest product from BioFactur, just introduced to the market a few days before printing this issue of bioplastics MAGAZINE, is a set of toy blocks. Like most of their other products BioFactur sells them through two large mail order businesses, Memo and Waschbär, both strongly committed to sustainable products. In addition all products are available via BioFactur’s own online-shop. The company is planning to launch about two or three new products each year – mostly toys or household items. Being asked what pioneers such as BioFactur expect from bioplastics resin suppliers and from politicians, Swoboda said that first of all he hopes for a decrease in raw material prices. “With raw material costs 30% above tradtional plastics it is not so easy”, he said. He sees his growth potential in a sustainable commercial market. Swoboda makes it clear: “The advantages of bioplastics must be communicated very strongly, and here too we need the policy makers.” MT www.biofactur.de

Injection Moulding

Pitcher with separate bamboo handle

ell Water (Reeuwijk, The Netherlands) recently announced that the patented and stylish Well Jug pitcher with its crystal clear Ingeo bioplastic pitcher and removable bamboo handle is now being made available to hotels, restaurants, food service organizations, and distributors for direct-to-consumer sales in the U.S. The Well Jug has been sold in Europe for the past year and with every unit purchased Well Water provides 264 gallons (1,000 liters) of clean drinking water to a village in Africa or Asia. Well Water has been giving 25% of the gross income from its bottled water business to charities since 2003. Several years ago, when the Dutch government launched a campaign to promote the use of tap water in order to reduce packaging, Well Water launched what would become a two and a half year research and development project into the Well Jug. The idea was to promote sustainability in the hospitality and food services industry with a reusable and sustainable cold drinks pitcher, while expanding efforts in Africa and Asia to bring fresh water to rural villages. The company is still working out how the sales of the Well Jug in the U.S. will figure into its drinking water and other charitable efforts. The Well Jug consists of a durable crystal clear injection molded Ingeo PLA 1 liter (1.06 quart) pitcher. To achieve the Well Jug’s crystal clear appearance with no flow marks was a balancing act in injection molding dependent on finding the optimum thickness for the pitcher’s walls.The removable handle is made from solid bamboo, one of the world’s fastest growing grasses. The handle can also be used by hotels, restaurants, or foodservice organizations to hold table announcements cards. Well Jug pitchers and handles are ultra-light, stackable, and require minimal transport and storage space. These pitchers are suitable for water, beer, juices, and other cold drinks and are hand washable in warm water. “The uniqueness of the Well Jug comes from its striking design, its utilization of sustainable materials, and the contribution of clean water to villages in Africa and Asia,” said Michel Rijkaart, director of sales and a principal/founder of Well Water. “The Well Jug on any table, whether it’s in a hotel or at a catered event, generates greater awarness and conversation about sustainable innovations.” Well Jugs can be customized with an orgnaization’s name and can be purchased in various colors. Hospitality, foodservice organizations, and distributors for direct-to-consumer sales interested in learning more about the innovative Well Jug may contact Michel Rijkaart directly.

www.welljug.co.uk www.wellwater.nl

bioplastics MAGAZINE [03/13] Vol. 8

Injection Moulding

Liquid wood and more… by Lars Ziegler Jürgen Pfitzer Helmut Nägele Benjamin Porter Tecnaro GmbH Ilsfeld-Auenstein, Germany

Fig. 1: Green Lantern, Romolo Stanco

ounded in 1998, TECNARO GmbH develops, produces and markets bio-based and biodegradable compounds. Focusing on thermoplastic compounds made from renewable resources like lignin, cellulose, natural fibres, PLA, PHB, Bio-PE, Bio-PA and others, Tecnaro has been developing solutions for injection moulding, compression moulding, extrusion, calendaring, blow molding or thermoforming into moulded parts, semi-finished products, sheets, films or profiles.

One of the raw materials mentioned is lignin, which is the second most abundant natural polymer after cellulose. More than 20 billion tonnes of lignin are generated naturally by photosynthesis per year. Lignin can be obtained as a by-product of the pulp and paper industry and the volume arising worldwide is about 50 to 60 million tonnes per year. Lignin can be extracted also from wood bark or straw. Mixing lignin with natural fibres like e. g. flax, hemp, wood or others and natural additives results in thermoplastic composites. These granules made from 100% renewable resources are named ARBOFORM® (arbor, Latin = the tree) and protected with various patent families. Besides Arboform , Tecnaro´s business is focused on two other compound categories: Biopolymer compounds ARBOBLEND® and natural fibre reinforced plastic composites ARBOFILL®.

ARBOFORM Arboform is sustainable, independent from crude oil, reduces environmental impacts and offers new markets for agriculture and forestry business. It combines two big industrial sectors: Wood industry can provide three dimensional parts in an economic way and plastics processors can substitute their materials by an ecological alternative. It can be considered as liquid wood.

ARBOFILL The compounds are made from plastics and natural fibers like wood, hemp, flex, sisal, bagasse from sugarcane, bamboo, coir fibre from coconut husk, etc. This combination offers sustainable and aesthetical materials with good mechanical and thermal properties at very competitive costs.

bioplastics MAGAZINE [03/13] Vol. 8

Injection Moulding Fig. 2: Bios line: Household series made from Arbofill with FDA approval, COZA

ARBOBLEND Arboblend can be 100% biodegradable or durable. It consists – depending on the grade - of biopolymers like the wood constituent lignin or of lignin derivatives and/or other biopolymers like polylactic acid, polyhydroxyalkanoates, starch, natural resins and waxes, cellulose, but also grades with sugar based Polyethylene and plant oil based Polyamides are available. The scope of material properties covers bio-compounds for injection moulding with very low up to very high Young‘s moduli of 100 to 16,000 MPa and high tensile strengths up to 100 MPa. Heat deflection temperatures (HDT-B) higher than 150°C are possible and impact strength can be modified to non-break (Charpy unnotched). New Arboblend grades include Thermoplastic Elastomers (TPEs) which can have biobased carbon contents of more than 90%. Compounds with following properties are already available: hardness in a range from 65 to 95 Shore A compression set below 45% tensile strength up to 8 MPa elongation at break up to 800%

Processing and Application Tecnaro´s approach as a specialized compounder is the optimal choice of polymers, fibres, fillers, processing aids and additives preferably from renewable and natural resources in order to achieve the required material properties and processability at lowest possible cost and environmental impact. Additives allow special functionalities and properties like flame resistance, UV stability and high impact strength. High heat deflection temperatures and impact properties can also be achieved by blending, fibre reinforcement and processing adaptations. Today’s series applications can be found in a wide range of products like e.g. household, toys, automotive, furniture, electronics, music instruments, packaging, stationary, building and construction industries as well as in funeral

business, agriculture and forestry. Until today, more than 200 series products have been realized so far. Due to free form geometries excellent designs can be achieved with Arboform. Low shrinkage grades allow precise tolerances in general without sink marks and very low warpage as well as a broad variation in wall thicknesses including thick-wall applications. Natural fibers are incorporated for reinforcement and sustainability reasons but also for special aesthetical designs: Injection moulded Arboform F results in surface appearances similar to root wood (see Fig 1). Arboform L and Arbofill have a regular visible fibre surface structure (see picture 2) which can be injection moulded without cloudiness or other typical moulding defects. Arboblend and Arbofill include grades which can be injection moulded into products with film hinges. Special Arboblend grades are available with Melt Volume Rates higher than 80 cm3/10 min. These are suitable for extreme thin-wall applications. Due to their low shrinkage and good bondage behavior several grades from all Tecnaro material families are suitable for Inmould Decoration IMD by back-filling of polymer and metal films as well as genuine wood veneers. According to a Tecnaro patent the latter can be moulded with overlap and therefore perfect intarsia can be realized without minimal gaps. Tecnaro´s bio-compounds can be chosen from an existing data base of already more than 2,000 formulations. For existing products and moulds the foreseen shrinkage and demoulding behavior as well as compatibility with hot runner systems, needle valves, etc. are taken into consideration. In case existing data seems not adequate for a new enquiry, modifications and new developments can be a suitable approach. Processing guidelines for each compound and technical assistance are provided for a successful start-up of serial production. www.tecnaro.de

bioplastics MAGAZINE [03/13] Vol. 8

From Science & Research

Lacquer from tomato for metal cans by D.ssa Angela Montanari, coordinator of BIOCOPAC project

16-hydroxyhexadecanoic acid HO

16Hid OH

10,16-dihydroxyhexadecanoic acid HO

16Hid-10ol OH

Fig. 4: Composition of tomato cutin

Introduction

very year millions of tons of tomatoes are used and large amounts of tomato by-products are treated as waste. About 300 million tonnes of by-products, waste and effluent are produced in the EU each year. Tomato waste consists essentially of the fibrous parts of fruits, seeds and skins, and can constitute as much as 2.2% of the weight of the processed tomato. The cost of disposing of these wastes is over 4 €/t. Currently tomato waste is used mainly for animal feed or, once it is dried, as the substrate for the production of fertiliser and lately for the production of biogas. Now BIOCOPAC, a project funded by the EU with € 800,000 under the 7th European Framework, is to develop a biobased lacquer for the protection of metal food packaging, using a natural biopolymer, cutin, extracted from peels and skins of industrial tomato by-products. The idea for the project is based on an old patent developed by SSICA (Stazione Sperimentale per l‘Industria delle Conserve Alimentari) in the 1940.

Lacquers for metal packaging The lacquers currently used are based on synthetic resins, mostly epoxy resins. However in recent years those synthetic lacquers have been the subject of several cases of alert due to problems of the migration of residues of polymerisation, monomers and oligomers, plasticizers added to the lacquering system or other additives. The object of the Biocopac project is to develop a natural based lacquer from the tomato skins. In this way Biocopac will meet the demand for sustainable

bioplastics MAGAZINE [03/13] Vol. 8

From Science & Research

Fig. 2: Dried tomato peels

Fig. 1: Separation of tomato peels and seeds from tomato waste

production and for the safeguarding of consumer health, increasing at the same time the competitiveness of the metal can industry, valorising waste produced by the food industry, reducing refuse and obtaining a product with high added value.

Analysis of tomato skins Tomato samples, collected in two tomato factories (one in Italy, one in Spain) have been subject to chemical and microbiological analysis. As the lacquer will be in contact with food products, the concentration of heavy metals and pesticides have been analysed. While tin (~ 80 ppb – parts per billion) and copper (4.9-11.8 ppb) were detected, other heavy metals were at values below the quantification limit of the measuring equipment. All samples analyzed for pesticide residues presented values below the significance’s limit.

Set-up of the extraction’s method The procedure of extraction of raw cutin from tomato peels consists in a treatment of skins with an alkaline solution and then cutin is separated through precipitation for successive centrifugation after a treatment with an acid solution. This procedure has shown very good results, with regard to the final product obtained, the yield and the reproducibility of the method as well as the applicability of the method even on an industrial scale. The final bioresin obtained with the extraction procedure showed a good ability to form a new bio-lacquer that is the target of Biocopac project.

Fig. 3: Raw cutin

The method has run not only in laboratory but also in a pilot plant with large quantities and high volumes. This is an important result for the project, as regarding a future application of the patent to industries. Naturally some improvements and modifications can be even studied and applied to obtain a continuous process.

Analysis of the cutin extracted The composition of tomato skins’ cutin has just been extensively studied in relation to the plant’s botany. Recently Graça [1] provided a tomato cutin consisting of n,16-dihydroxyhexadecanoic acids where the 10-isomer is largely dominant. The tomato cutin is a polyester biopolymer interesterificated. The significant proportion of secondary esters (esterification in the C-10 secondary hydroxyl) shows that the polyester structure is significantly branched.

Resin’s production The experimental work, in the consecutive phase, still in progress, has examined the production of the resin. For the production of the cutin-based resin two alternative methods are currently underway: Homopolymerization of the extracted raw cutin With the homopolymerization the cutin-based resin has been obtained from extracted cutin applying particular experimental conditions of polymerization; in this method the cutin polymerizes with itself to get a higher molecular weight resin.

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From Science & Research

Copolymerization of the extracted cutin with selected petrochemicals raw materials With the copolymerization some standard polyester resins have been copolimerized with the extracted raw cutin (10% and 20%) and the resultant resins have been characterized.

Development and application of the Biocopac lacquer Different formulations of lacquer containing from 10 to 100% of cutin have been prepared and characterized in order to find the best formulations for the final bio-lacquer. The more promising formulations have been applied on different metallic substrates (tinplate, tin free steel and aluminium) and some properties such as degree of curing, appearance, sterilization’s resistance were measured. The first results obtained with at least two formulations, showed good values of chemical resistance (MEK - Methyl Ethyl Ketone - test), good adherence (tape test), good mechanical properties and a good resistance to thermal sterilization in water.

Production of cans and caps Based on the first best formulations, sheets of tinplate and aluminium have been lacquered. From these lacquered sheets it has been possible to produce two piece cans, crown corks and caps. In all cases the lacquer didn’t show adherence’s loss, rather it has showed a good behaviour in all the products obtained as it can be seen in Fig. 5.

Conclusions All these first results are considered very satisfactory and from these first results the researchers are optimistic about the possibility of realize a natural lacquer and chances of getting a polymeric film obtained from tomatoes are becoming a reality.

[1] J. Graça and P Lamosa, ”Linear and Branched Poli (ω-hydroxyacid) Esters in Plant cutin”, J. Agric. Food Chem. 2010,58,9666-9674. [2] J.C. Saam, “Low temperature polycondensation of carboxylic acids and carbinols in heterogeneous media”, J. Polym. Sci., Part A: Polym. Chem.; 1998, 36, 341-356. [3] J.J. Benìtez, R. Garcìa-Segura, A. Heredia, “Plant biopolyester cutin: a tough way to its chemical synthesis”, Biochim. Biophys. Acta; 2004, 1674, 1-3. [4] J.A. Heredia-Guerrero, A. Heredia, R. Garcìa-Segura, J.J. Benìtez, “Synthesis and characterization of a plant cutin mimetic polymer”, Polymer, 2009, 50, 5633-5637 [5] D. Arrieta-Baez, M. Cruz-Carrillo, M. B. Gòmez-Patino, L. G. Zepeda-Vallejo, “ Derivatives of 10,16-dihydroxyhexadecanoic acid isolated from tomato (Solanum lycopersicum) as potential material for aliphatic polyesters”; Mol., 2011, 16, 4923-4936. [6] European patent application EP 2 371 805 A1 “Method for the application of oligo- and polyesters from a mixture of carboxylic acids obtained from suberin and/or cutin and their use thereof” published by VTT Technical Research Centre of Finland on the 5th November 2011. [7] Società Italiana Pirelli, Brevetto per invenzione industriale N° 389360 “Vernici a base di resina estratta dalle bucce di pomodoro” ,1944

A significantly more comprehensive version of this article with more results and details about the project can be downloaded from www.bioplasticsmagazine.de/201303

The project partners: Stazione Sperimentale per l’Industria delle Conserve Alimentari (IT – RTD Performer) Centro Tecnologico Agroalimentario Extremadura (ES – RTD Performer) Fundacion TECNALIA Research & Innovation (ES – RTD Performer) SYNPO A.S. (CZ – RTD Performer) Salchi Metalcoat S.r.l. (IT – lacquer manufacturer) Chiesa Virginio Azienda Agricola (IT – livestock & biogas producer) Conservas Martinete S.A. (ES – manufacturer of canned tomato)

www.biocopac.eu

National Can Hellas S.A. (GR – metal packing) Rodolfi Mansueto S.p.A. (IT – transformation of tomatoes) Schekolin AG (LI – manufacturer of lacquers)

Fig. 5: Samples of cans and caps lacquered with varnish.

bioplastics MAGAZINE [03/13] Vol. 8

Saupiquet S.A.S. (FR – canned seafood producer)

THE NO. 1 FOR WORLD PREMIERES: K 2013 Get ready for your most important global business and contact platform. On a net exhibition space of more than 168,000 sqm, some 3,000 exhibitors from over 50 countries will be presenting innovative solutions and visionary concepts in the areas of machinery and equipment, raw materials and auxiliaries, semi-finished products, technical parts and reinforced plastics. Plan your visit now. Welcome to your K 2013.

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www.messe-duesseldorf.de

From Science & Research

Bioplastic products from citrus wastes

by Mohammad Pourbafrani1 Jon McKechnie2 Heather L. MacLean1,3 Bradley A. Saville1 1

Department of Chemical Engineering and Applied Chemistry, University of Toronto, 200 College Street, Toronto, ON, M5S 3E5, Canada

Division of Energy and Sustainability, University of Nottingham, University Park, Nottingham NG7 2RD, UK

Department of Civil Engineering, University of Toronto, 35 St George Street, Toronto, ON, M5S 1A4, Canada

Introduction:

iomass-derived plastics have the potential to displace relatively high market value products, while also contributing to sustainability objectives. In particular, second generation feedstocks such as agricultural residues offer great potential. Employing citrus wastes (CW) as a feedstock for bioplastics production has potential as a low-cost alternative, while providing other environmental advantages. Approximately 30 million tonnes of CW is estimated to be produced annually, representing half of the citrus fruit used for juice production [1]. New strategies for processing CW are required to address disposal challenges, including high costs, a lack of disposal sites, and concerns about negative environmental impacts of current practices. Citrus waste contains simple sugars and carbohydrate polymers such as cellulose and hemicellulose. The proposed CW biorefinery discussed in this article could convert these sugars and carbohydrates into bioethanol, while recovering limonene (natural solvent), and producing biomethane and nutrientrich digestate (fertilizer) from residual materials [1]. The bioethanol could then be further processed to renewable low density polyethylene (LDPE) following ethanol dehydration to ethylene. To evaluate the CW to LDPE process, it is important to understand the associated environmental implications from a life cycle perspective (from feedstock production through to the final product) and to compare with current production technologies. Understanding the greenhouse gas (GHG) emissions of the process is important due to the GHGintensity of current LDPE production from fossil fuels. In this article, the potential to reduce life cycle GHGs when LDPE is produced from citrus wastes is evaluated.

Citrus waste to bioethanol A biorefinery for production of bioethanol from CW is presented in Fig.1. The technical data related to the

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From Science & Research

Citrus Waste

Hydrolysis Reactor

Flash

Limonene Recovery

Limonene

Biogas Purification

Methane

Acid

Methane Fermentation

Ethanol Distillation

Liquid

Flash

Solid

Stillage

Anaerobic Digestion

Steam Boiler

Steam

Citrus Waste Biorefinery

Ethanol

Power Plant

Electricity and Heat

Ethylene and LDPE Production Plant

Excess to grid LDPE

Limonene and Digestate

Fig. 1. Block Flow Diagram of Ethanol Production from Citrus Wastes [1]

Fig.2. Production of LDPE from Citrus Wastes

biorefinery were published previously [1]. The biorefinery’s main stages include hydrolysis, fermentation, distillation and anaerobic digestion. Citrus waste carbohydrate polymers are converted into sugars during hydrolysis, and then fermented to produce bioethanol. The ethanol is purified by distillation and the non-fermentable sugars and other process residues are converted to biomethane by anaerobic digestion. Some of the biomethane is combusted to satisfy the thermal energy requirements for the biorefinery; excess biomethane is converted to electricity. In this biorefinery design, one dry tonne of CW yields 198 liters of ethanol, 45 liters of limonene, 270 m3 of biomethane and 220 kg digestate. For a hypothetical 40,000 dry tonne per year CW biorefinery, the ethanol production cost is estimated to be 0.65 USD per litre [1].

A life cycle assessment was performed to calculate the life cycle GHG emissions associated with LDPE production from CW. The key inputs, outputs and processes are shown in Figure 2, and include CW transportation, bioethanol production, ethylene production and LDPE polymerization. The emissions associated with LDPE production include all process steps, inputs and outputs. In addition, emissions credits resulting from the biorefinery’s co-products (limonene, digestate and biomethane) displacing chemical and fossil fuel products (acetone, biofertilizer and natural gas, respectively) are assigned to the LDPE. This method of co-product treatment, termed displacement or system expansion, is recommended under the International Organisation for Standardisation guidelines for life cycle assessment [3].

Bioethanol to bioplastic The ethanol produced by the CW biorefinery is dehydrated to ethylene in a catalytic process at high pressure and temperature [2]. Each kg of ethanol yields 0.59 kg of ethylene. This process is energy intensive and requires 5.6 MJ of thermal energy and 1.8 MJ of electricity per kg of ethylene produced. The ethylene is polymerized to LDPE, consuming 0.3 MJ of thermal energy and 6.4 MJ of electricity per kg of LDPE. With 1 kg of ethylene yielding 1 kg of LDPE, each dry tonne of CW can produce ~92 kg of LDPE.

Life Cycle Assessment of renewable LDPE from citrus wastes Although LDPE production from CW is an energy intensive process, biomethane generated in the biorefinery can provide the required energy (Fig. 1 and Fig. 2). The biomethane is utilized in a power plant that generates heat and electricity, which are consumed by the ethanol and ethylene production processes and the ethylene polymerization process; excess electricity is exported to the grid. Therefore, the production of LDPE from CW is energy self-sufficient.

Since generation of electricity and heat from biomethane is considered to be a carbon neutral process, the life cycle GHG emissions of LDPE production are dominated by chemical inputs to the process stages, fossil fuel use in transportation of CW to the biorefinery, and biomethane emissions from the biorefinery’s anaerobic digesters [4]. The net life cycle emissions for the production of renewable LDPE are -4,100 g CO2eq./kg. Negative emissions are achieved because of two factors: CW LDPE sequesters biomass carbon that would otherwise be released to the atmosphere; and emissions credits for co-products more than offset the production-related emissions. By comparison, the life cycle GHG emissions values for LDPE produced from crude oil are significantly greater (2,130 g CO2eq./kg of LDPE) [5]. Prior work has assessed LDPE production from sugar cane [2], which found emissions to exceed those of crude oil-derived LDPE when including land use change-related emissions (e.g., land clearing directly or indirectly linked to sugar cane cultivation for ethanol production). In contrast, when using CW, no land use change related GHG emissions are incurred since CW is a byproduct of juice manufacture.

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From Science & Research

Financial considerations Ongoing work will evaluate the financial performance of the above CW biorefinery system. Based on recent market prices for ethanol and LDPE [6, 7], process costs for converting ethanol to LDPE would have to be less than ~$0.20/kg LDPE to offer a competitive use of ethanol without subsidy. The financial attractiveness of LDPE production from CW is affected by the high market price of ethanol, which results in part from existing policies that mandate its use as a transportation fuel. Currently, similar support is not available to biomass-derived chemicals or plastics.

Summary Conversion of CW to renewable LDPE is demonstrated to have the potential to significantly reduce life cycle GHG emissions compared to LDPE produced from fossil fuel or sugar cane. Utilizing global CW supply for producing LDPE would provide up to 3.5% of worldwide demand [8] and reduce emissions by approximately 3.4 million tonnes CO2eq./yr, while simultaneously addressing environmental concerns related to CW disposal practices.

[1] Pourbafrani M., 2011. Citrus Waste Biorefinery: Process Development, Simulation and Economic Analysis. PhD Dissertation. Published by Chalmers University of Technology. Gothenburg. Sweden. [2] Liptow C., Tillman A.M., 2009. Comparative Life Cycle Assessment of Polyethylene based on Sugarcane and Crude Oil. Report No.2009:14. Published by Chalmers University of Technology. Gothenburg. Sweden. [3] ISO 14044 (International Organisation for Standardisation) 2006 Environmental Management—Life Cycle Assessment— Requirement and Guidelines [4.] Pourbafrani M., McKechnie J., MacLean L.H., Saville A.B., 2013. Life Cycle Greenhouse Gas Impacts of Ethanol, Biomethane and Limonene Production from Citrus Waste. Environmental Research Letter, 8, 015007 doi:10.1088/1748-9326/8/1/015007 [5] PlasticsEurope, 2008. Low Density Polyethylene. http://www. plasticseurope.org/plastics-sustainability/eco-profiles.aspx (accessed 15/04/2013) [6] NASDAQ, 2013. Ethanol Futures. http://www.nasdaq.com/ markets/ethanol.aspx (accessed 15/04/2013) [7] Platts, 2013. Platts Global Low-Density Polyethylene Price Index. http://www.platts.com/newsfeature/2013/petrochemicals/pgpi/ ldpe (accessed 15/04/2013) [8] Nexant, 2010. Polyolefins planning service: Executive report, Global commercial analysis. http://www.chemsystems.com/ about/cs/news/items/POPS09_Executive%20Report.cfm (accessed 15/04/2013)

www.utoronto.ca www.nottingham.ac.uk

Big enough to innovate, small enough to cooperate!

It takes sophisticated technology to make plastics recycling sustainable and more efficient and to continuously improve pellet quality. And it takes commitment to really be successful. SIMPLY ONE STEP AHEAD

www.ngr.at 30

bioplastics MAGAZINE [03/13] Vol. 8

Chinaplas Review

Chinaplas 2013 took place from May 20 - 23 in the southern Chinese city of Guangzhou, being Asia’s No. 1 and the world’s no. 2 plastics and rubber exhibition. More than 2900 exhibitors from 38 countries showed their expertise on 220,000 m² of floor space. Chinaplas expected to attract more than 115,000 Chinese and foreign visitors from 150 countries looking to learn about, exchange and source chemicals and raw materials and a variety of plastics and rubber machinery. In a special Bioplastics Zone in hall 12.2 again more than 30 companies were listed in the show catalogue to present their products and services in terms of biobased and/or biodegradable plastics. Still there were a significant number of companies offering traditional PE or PP filled with starch, straw or bamboo and it could be argued whether or not such blends should be considered as bioplastics.

The 5th International Seminar on Bioplastics Applications took place on May 18-19 in a Guangzhou hotel, sharing the latest trends, government policy on bioplastics and lowcarbon economy, and the technologies of the bioplastics industry. Key material suppliers, manufacturers, professional research organizations and machinery suppliers were invited to offer their expertise. As in previous years, the booth of bioplastics MAGAZINE was very well visited. We had lots of interesting talks and many visitors seriously interested in bioplastics. The 1000 copies of bioplastics MAGAZINE that were printed specially for this show were gone after two and a half of the four very busy days at Chinaplas. In addition to the Chinaplas Preview that we published in the last issue, we now add some more small reports about selected companies from the Bioplastics Zone in Guangzhou.

Hubei Guanghe Bio-technology Co., Ltd. Since 2006 Hubei Guanghe Bio-technology has been engaged in the development of ultra-high molecular weight PLA compounds in cooperation with different universities and colleges. At Chinaplas they presented four different grades: GH401 for injection moulding, GH501 for sheeting, GH601 for stretch blow moulding and GH701 for film. Products made from the GH materials include disposable tableware, hotel consumables, agricultural applications and bags. All GH reins are OK-Compost certified (EN 13432). www.ghbt.com.cn

Jiangsu Jinhe Hi-tech Co., Ltd This company is located in Yangzhou (Jiangsu province) near Shanghai. The main products are starch and straw filled polypropylene. The materials are well suited for injection mouding of high quality products such as cutlery, plates and bowls or even coat hangers, child chairs and toothbrushes. www.jsjhgk.com

Guangzhou Bioplus Materials Technology CO., Ltd Bio-plus Materials Technology is specialized in the development of modified PLA. The predecessor, Junjia Technology Co., Ltd., was founded in 1998 and in 2006, the company started to step into the field of modified PLA and its application. Their current focus is on property improvement of PLA, especially on heat resistance and impact strength. By now, we have already made great progress on its heat resistance. Bioplus’ products include grades for injection moulding and such for extrusion and thermoforming with heat deflection temperatures up to 100°C without inorganic filers and such with white inorganic fillers. Special grades for foam appications and for bottle blowing as well as such for melt spinning are also available. www.bio-plus.cn

bioplastics MAGAZINE [03/13] Vol. 8

Chinaplas Review ITENE

Shandong Fuwin New Material Co. Ltd.

The Spanish Packaging, Transport & Logistics Research Center ITENE is a Technological Center that promotes, in general and for any type of business, scientific research, technological advancement, the development of information society and promoting sustainability in the areas of packaging, logistics, transportation and mobility. Now ITENE presented itself in the Bioplastics Zone at Chinaplas. Among other products and services they showed blends of PLA and nano-clay. These products were developed in order to enhance mechanical and barrier properties.

Shandong Fuwin New Material Co. Ltd., from Zibo Shandong is primarily engaged in the production and R&D of fully biodegradable plastic materials and fine chemicals. Their products include BDO, PBS and PBS co-polymers and are marketed under the brand name ECONORM. Fuwinâ&#x20AC;&#x2122;s capacity for the production of PBA and PBSA is about 25,000 tonnes/annum. Their materials are made with biobased succinic acid and currently still with fossil based BDO. Injection moulding grades (e.g. for disposable cutlery, plant pots etc) are available as well as blown film grades e.g. for shopping bags or mulch film.

www.itene.com

DuPont The RS product range of DuPont (RS for renewably sourced) is well known. It comprises among other products the long-chain Zytel RS polyamide 1010, the elastomer Hytrel RS and the PTT material Sorona. While the PA 1010 offers different properties and functionalities compared to PA 11 or PA 12, the Hytrel RS elastomer is a drop-in material with the same properties as the oil based Hytrel. Here it is important for customers that the biobased version is not more expensive. Sorona is not very much used in China, but the Japanese automotive company Toyota recently decided for an air outlet in the instrument panel of the Prius model for Sorona. This saved cost compared to PBT or PA6. Not due to the resin price, but due to the fact, that the PTT version did not need to be painted in a secondary step. With an R&D center in Shanghai and compounding plant in Shenzhen DuPont offer their clients comprehensive consultation in the development of applications. www.dupont.com

Fukutomi The core business of Fukutomi Company Ltd. From Shantou, China, is the production of plastic parts from plastic scrap. To prove their commitment to environmental protection and to follow the companyâ&#x20AC;&#x2122;s objective of sustainable development, Fukutomi also started to produce PLA compounds as well as parts from PLA. Fukutomi has produced products such as ice cream spoons, golf tees and flower pots from Biodegradable Polylactic Acid. The PLA compounds include grades for injection moulding, bottle blowing and sheet grades.In order to meet the customers growing requirements, Fukutomi provide PLA material modification, mould design and production service. www.fukutomi.com

bioplastics MAGAZINE [03/13] Vol. 8

www.sdfuwin.com

Nafigate Nafigate Corporation a.s. from Prague (Czech Republik) presented their biotechnology for PHA production that was developed by (Czech) Brno University of Technology. Nafigate is now seeking to find partners to invest into this technology. The distinctive feature of the technology is that it uses waste cooking oil as the raw material und thus does not compete in any way with food or feed.production. The high performance bioprocess for the production of PHA assures lower operational cost and market price, as a spokesperson told bioplastics MAGAZINE. A model calculation for a 10,000 tonnes/annum plant shows the potential to achieve a market price of EUR 2.1 (USD 2.8) per kg of raw material. www.nafigate.com

Shenzhen Esun Industrial CO., Ltd. Established in 2002 and located in Shenzhen Special Economic Zone, Shenzhen Esun Industrial Co., Ltd. is a high-tech enterprise specializing in researching, developing, producing and operating degradable polymer materials, such as PLA and PCL. The company strives for becoming the leader in biodegradable material industry and achieving the breakthrough of 200,000 tonnes annual capacity within the next ten years. One of the highlights at Chinaplas is the new PLA sheet material for the production of cards: membership cards, gift cards, etc. www.brightcn.net

Chinaplas Review Tianjin GreenBio Materials Co., Ltd

Grabio Greentech Corporation

GreenBio is dedicated in the development, production and sale of the fully degradable bio-based polymer materials PHA and its application products. So far GreenBio has established the worlds largest production base of PHA in the Binhai District in China (capacity 10,000 tonnes/ annum). The PHA materials are marketed under the brand name Sogreenâ&#x201E;˘. Among other products GreenBio have developed exclusive PHA foam pellets. This kind of foam pellets have over 20 times in expansion and can be made into full-biodegradable foam food service ware and industry or electric appliance packaging to replace conventional EPS. As highlights at Chinaplas the company presented heat stretch film and nonwoven fibre products.

Grabio Greentech Corporation specializes in the development and manufacture of 100% biodegradable and compostable starch plastics. Their products are GRABIO film grade resin and GRABIO agri grade resin. Grabio starch plastics are all certified (EN 13432 and ASTM D6400) compostable. At Chinaplas Grabio displayed its existing GB series film grade products, among which a newly developed GBL series film grade material was also on display. The new GBL series material has more rigid texture and higher renewable content, and is suitable for making shopping bag, fruit bag, magazine wrapping and other flexible packing applications. Moreover, besides the GB and GBL series, the developing GBXV series material is designed for high transparency require packaging application.

www.tjgreenbio.com

Toray

www.grabio.com.tw

Toray Industries Inc. headquartered in Tokyo, Japan, offers a range of different products under the common brandname ecodear. This includes blends of PLA with ABS (offering higher strength), blends of PLA with PC (with enhanced flame retardance) and PLA blends with PMMA offering an excellent transparency in combination with heat resistance. Other members of the ecodear family are a PA 610, a bio-Polyethylene foam based on Braskem Green PE and a partly biobased PBT, made with bio-BDO. www.toray.co.jp/english/plastics

Shanghai Disoxidation Macromolecule Materials Co., Ltd With the mission of Life &Environment Balance and Natural, No Harm, Shanghai Disoxidation Macromolecule Materials Co., Ltd (DM) is providing plastic manufacturers and consumers with biodegradable starch resins and related derivatives, such as shopping bags, garbage bags, films and outside package. The company is located in Xiangshi Road Jin Ban Industrial Zone of Kunshan, Jiangsu Province and runs 10 Coperion dual screw extruders, automatic feeding and packaging. DM have a capacity of 32, 000 tones/year. Their product BSR-09 was developed for blown film application and is EN 13432/ASTM 6400 certified compostable. www.dmmsh.com

bioplastics MAGAZINE [03/13] Vol. 8

Application News

Biobased barrier packaging for cheese As part of a diploma project on the subject of “Ecologically sustainable packaging in the food industry” the Ecological Dairies at Allgäu (ÖMA – Ökologische Molkereien Allgäu) worked closely together with Plantic Technologies GmbH (the German branch of Australian Plantic Technologies Limited) on the basic concepts of using sustainable packaging materials. After an extensive series of product tests the cheeses specialists, who consistently focuses on ecological products, decided in February 2013 to try a new approach to the packaging question and from April used Plantic eco Plastic™ for the first time for their pre-packaged sliced cheese. Plantic eco Plastic was developed to replace petroleumbased plastics with bioplastics in the food industry. It is the first barrier packaging in the world that is biobased up to 80% from renewable resources. The thermoform sheet consists of a three-layer structure with the Plantic core layer being up to 80% of the total film thickness and having particularly good barrier properties, as explained to bioplastics MAGAZINE by Brendan Morris CEO at Plantic. “It is embedded between two very thin layers of polyethylene which also contributes to the excellent sealing performance of the laminate film. The new biobased lidding film will come in the next few months”. During the production process up to 50% less energy is used when compared with conventional polymers, and Plantic eco Plastic can offer this material, which is so important for food packaging, in good quantities. “That was an important step in the right direction, and underlines our company philosophy. We aim for ecological progress and high quality. In both areas, using the new packaging, we have made a significant step forward”, said Michael Welte, CEO of ÖMA. “As the first German supplier of bio-cheeses we have now developed a sustainable packaging solution for our bio-cheese slices that also supports the product’s freshness.” “At the time of the changeover we had two main problems”, continued Michael Welte. “Firstly we had to ensure that the maize-based packaging we were using was totally free of any genetically modified products, and secondly, since our product places high demands on the barrier performance of the packaging material it was important that our project partner Plantic Technologies, was able to offer a material that would not allow any loss of quality or taste”. “We were able to confirm this within the extensive product test programme that was carried out”, said Brendan Morris. MT www.oema.de www.plantic.eu

bioplastics MAGAZINE [03/13] Vol. 8

Bicycle mudguards

Zéfal (Jargeau, France) is the world’s leading manufacturer of bicycle accessories. Innovation and environment play a significant part in the corporate strategy and eco-design of the products is part of a longterm progress undertaking. Zéfal launched its bio-based range Green’Z with a low carbon footprint at the Eurobike show in 2012. This range, the first in the world, comprises the Green’Z Deflector FC50 & RC50 mudguards made with plant-based plastic. To this end Zéfal selected Gaïalène® (by Roquette) on account of its certified environmental qualities and its possible recyclability at the end of life. This plastic has turned out to be easy to use with slight manufacturing process adjustments and has enabled a reduction in the consumption of electricity used by the injection machines. ‘’Focused on the future our teams who are passionate about their work innovate every day in order to improve the practice of cycling. The strong links we have forged with the cycling community and the bicycle distributors inspired the creation of this Green’Z range”, explains Mathieu Brunet, the Chairman and Chief Executive of Zéfal. This initiative enables Zéfal to propose a range of products that constitute a breakthrough from an environmental standpoint, while retaining the same manufacturing quality that the customers are used to. The mechanical and ageing tests have confirmed the suitability of this material for these applications linked to sport and nature. The result is a carbon footprint reduced by over 65% compared with the products usually made from polypropylene, without any compromising on the technical or economic performances. Zéfal is consequently going to pursue this initiative with several products in its range and intends in the coming years to develop the Green’Z brand by innovating in other complementary applications. MT www.zefal.com www.gaialene.com

Application News

First PA 410 film introduced DSM Engineering Plastics (since early 2012 headquartered in Singapore) recently announced that its development partner MF Folien GmbH in Kempten, Southern Germany, successfully introduced a new polyamide film, which is based on DSM’s bio-based EcoPaXX® polyamide 410. MF Folien is a leading expert in the production of polyamide film, and has been DSM’s development partner for EcoPaXX film from the start. In 2011, the company was the first to create samples of 30 µm cast film from EcoPaXX. This film has the same high quality level for which MF Folien is very well known in the market. Samples of film based on EcoPaXX are available in various thicknesses: 30, 40 and 50 µm. Potential application areas are in flexible food packaging, building & construction, medical, aviation and shipping.

Recently, three grades of EcoPaXX were given the “Certified Biobased Product” label (70%), awarded by the United States Department of Agriculture (USDA). The bio based content of EcoPaXX polyamide 410 stems from one of its building blocks, derived from castor oil obtained from plants that grow in tropical regions and which are not used for food products. MT www.dsm.com www.ecopaxx.com www.mf-folien.de

Rainer Leising, general sales manager MF Folien, said: “We are delighted to be working with DSM on the development of this innovative and sustainable material solution. Since we first introduced EcoPaXX film, with its distinctive shiny, silvery ‘high-tech’ appearance, the material has been featured in our product brochure.” EcoPaXX polyamide 410 films are strong and transparent with a high puncture resistance. They have a reduced moisture transmission rate versus polyamide 6 film, and a comparable oxygen barrier. When fully wet, the oxygen barrier of polyamide 410 is even higher.

PLA serviceware in Asia Purac’s partners have successfully launched a range of PLA serviceware based on PURALACT® Lactides. The range, available in retail outlets in Singapore, features printed text ‘Love Eco’ and ‘PLA’ on each item. The packaging includes a variety of sustainability and performance statements, including: dishwasher safe microwave safe

The serviceware is being produced by New Sunrise Plastics Co and is retailed at Giant Hypermarket in Singapore. Puralact Lactide monomers for PLA are exclusively made from non-GMO feedstocks, heat resistant up to 120°C, biobased, biodegradable & recyclable. www.purac.com/bioplastics www.srplastic.com

food contact approved (USA & Europe) biodegradable.

bioplastics MAGAZINE [03/13] Vol. 8

From Science & Research

Advances in PLA chemistry

by Alexander Hoffmann Sonja Herres-Pawlis Ludwig-Maximilians University Munich, Germany

New robust catalysts for lactide polymerization: Zinc complexes of neutral nitrogen donors

ing-opening polymerisation (ROP) of lactide represents a growing field of research because the resulting polymers are biodegradable and based on renewable raw materials which ensures growing attention within the context of Green Chemistry. Up to now, neutral nitrogen donor ligands have been overlooked in their potential to stabilise catalytically active systems. This contribution highlights recent developments in this area as well as the applicability in the lactide polymerisation with special regard to the reaction conditions. Targeting a use in industrial scale, the tolerance towards moisture, air, lactide impurities and high temperatures is an important issue to be considered during catalyst design. For the well-controlled synthesis of polylactide with regard to composition, molecular weight and microstructure, the coordination-insertion process is now commonly regarded as the most efficient method [1-4]. This mechanism (Figure 1) involves the coordination of the monomer to the metal centre, followed by a nucleophilic attack of the alkoxide to the acyl carbon atom and the insertion of lactide into the metalalkoxide species with retention of configuration [5]. A new metal-alkoxide species is formed which is capable of further insertion reactions. Under industrial conditions, mostly homoleptic catalysts are used like tin(II)ethylhexanoate, zinc(II)lactate and aluminium isopropoxide in combination with alcohols as initiators [6]. These catalyst systems can be conveniently synthesised and utilised in the polymerisation of cyclic esters but complicated equilibria phenomena and multiple nuclearities of the active species result in limited polymerisation control. Detrimental side reactions like transesterifications and epimerisations may occur which lead to a broadening of the

bioplastics MAGAZINE [03/13] Vol. 8

molar mass distribution. Consequently, the development of new catalysts for the ring-opening polymerisation of lactide has seen tremendous growth over the past decade [1-5,7]. As amelioration, these catalysts shall enable a better control, activity and selectivity during the polymerisation by optimal adaption of the coordinating ligands. A vast multitude of well-defined Lewis acid catalysts following a coordinationinsertion mechanism has been developed for this reaction mainly based on tin,[8] zinc,[9-12] aluminium[13-15] and rare earth metals [16-20]. To develop the polymer from a specialty material to a large-volume commodity plastic the development of new polymerisation catalysts is required. Most large-scale processes are based on the use of stannous compounds as initiators [3,4,7]. For use in food packaging or similar applications, heavy metals are undesirable because of accumulation effects [3,4]. To date, the design of new catalysts mostly follows the paradigm that an efficient lactide ROP initiating system needs an anionic ligand, e.g. alkoxides, amides, ketiminates or an alcohol as co-initiator which forms the truly active species as alkoxide. The high polymerisation activity of all these systems is often combined with high sensitivity towards air and moisture. For industrial purposes and especially the breakthrough of PLA in the competition with petrochemical based plastics, there is an exigent need for active catalysts that tolerate air, moisture and small impurities in the monomer [3,4,7]. The disadvantageous sensitivity can be ascribed to the anionic nature of the ligand systems stabilising almost all of these complexes.

From Science & Research

the use of the sterically less demanding guanidine-pyridine ligands, a multitude of zinc complexes could be isolated and trends for the ROP activity were derived [29,30]. In case of the quinoline-guanidine complexes, mono(chelate) chlorido complexes exhibit smaller activity than the mono(chelate) acetato complexes [29,30]. Especially quinoline-guanidine bis(chelate) triflato zinc complexes exhibited very high activity and robustness towards monomer impurities at the same time. Using technical quality lactide, molecular weights of 70000 and 77000 g mol-1 (Mn) with PDs of 2 could be obtained with conversions of >90% [29,30]. Together with comparative studies with guanidine mesylato complexes,[31] it came up that within the bis(chelate) triflato zinc complexes the zinc atom possesses a high positive partial charge and the guanidine a pronounced negative charge.

Figure 1. Coordination-insertion mechanism for lactide ROP

The role of neutral donor ligands for the stabilisation of ROP active systems has to be highlighted because this niche has been overlooked for years [21]. With regard to industrial usefulness, only systems with real applicability in lactide bulk polymerisation are discussed here (Figure 2). The scope of used neutral N donors ranges from simple alkylated amines and substituted pyridines over guanidines to sophisticated oxabispidines and oxalamidines. Historically, the pyridinecarbene zinc complexes of Tolman and coworkers are the first complexes of this class; they polymerise lactide at 140°C within minutes with a polydispersity (PD) of 2.4 [22]. The robust 9-oxabispidine zinc acetate complex has been reported as ROP active system in the lactide melt at 150°C (PD = 2) but with low yields [23]. As rather simple neutral ligand systems, the classic N donor ligands 2,2´-bipyridine and 1,10-phenanthroline were proven to stabilise zinc complexes with surprising ROP activity under challenging conditions in melt in 2009 [24]. The polydispersities of approximately 2 account for the presence of transesterification reactions. In order to overcome the limitations of anionic and other sensitive ligand systems, the potential of a neutral but highly nucleophilic ligand system was evaluated. Guanidines convince by their good donor properties and their strong nucleophilicity [25,26]. In 2007, the first cationic complex [Zn(DMEG2e)2][OTf]2 comprising an aliphatic bis(guanidine) has been reported as active ROP catalyst for the lactide polymerisation in melt at 150°C [27]. In following studies with the closely related but more basic imino-imidazoline 8MeBL, it appeared that the partial charge at the zinc atom as well as on the donating Nimine atom is crucial for the lactide activity [28]. Using mono(chelate) zinc imino-imidazoline complexes high conversions of 88 % were observed. With

As guanidines are strong neutral donors, their nucleophilicity was proposed to help the ring-opening reaction. In all these polymerisation experiments with commercial grade PLA, no external initiator had been added. Hence, the working hypothesis implied the coordination of the lactide to the zinc centre followed by a nucleophilic attack of the guanidine on the carbonyl C atom of the lactide molecule. Guided by this idea, extensive density functional studies for the ROP with guanidine triflato zinc complexes were accomplished [32]. In fact, this computational study is the first DFT study for the ROP with neutral ligands without additional co-initiators. The fluorescence activity of the guanidine-quinoline ligands gave further mechanistic hint because the quinoline-related emission can be traced in the zinc complexes and the resulting polylactide. Moreover, the UV absorption of the guanidine-quinoline ligands was found in the corresponding lactide as well [32]. In summary, these studies showed that the guanidine zinc triflato complexes react in a variant of the coordination-insertion mechanism with the nucleophilic attack to the lactide performed by the guanidine and the classic ring-opening step as next transition state [32]. The great impact of the guanidine is expressed in two central traits: the excellent donor capacity stabilises very robust zinc complexes and the high nucleophilicity of the guanidines enables the ring-opening of cyclic esters by the guanidine donor functionality. The great advantage of guanidine systems is their extraordinary robustness towards moisture and monomer impurities. Until now, comparable robust systems have only been reported by Davidson et al.[33] who used tris-phenolate titanium complexes. However, the zinc guanidine systems combine in a unique manner many crucial features for efficient large-scale lactide ROP. In detail, the robustness of zinc guanidine complexes in lactide ROP supersedes monomer recrystallisation or sublimation and saves cost-effective processing steps. Moreover, the polymerisation can be accomplished under melt conditions at high temperatures up to 200°C without racemisation effects [32]. This is important for further applications in reactive polymer extrusion.

bioplastics MAGAZINE [03/13] Vol. 8

From Science & Research

Figure 2. Selected catalysts with neutral donor ligands magnetic_148,5x105.ai 175.00 lpi 45.00° 15.00° 14.03.2009 75.00° 0.00° 14.03.2009 10:13:31 10:13:31 Prozess CyanProzess MagentaProzess GelbProzess Schwarz

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Targeting simpler and cheaper donor systems, very recently, zinc complexes of peralkylated amines came into the focus of research: they are derived from lowpriced starting materials and convince by high ROP activity at 150°C to molecular weights of 65000 g mol-1 at PD of 2 [34,35]. Parallely, the donor class of oxalic amidines has been investigated for the stabilisation of zinc complexes in the polymerisation of lactide which opens up a new neutral N-donor ligand class [36]. An oxalic amidine zinc chlorido complex yields polylactide with 50000 g mol-1 at PD of 1.4. The comprehensive concept of robust N donor zinc systems has been proven to yield efficient and versatile ROP active catalysts. In general, the importance of neutral ligands for the ring-opening polymerisation of lactide cannot be underestimated. With regard to the major breakthrough of bioplastics for the substitution of petrochemical plastics in the commodity market, every robust catalyst system represents a huge step towards greater sustainability of our society. www.cup.lmu.de/ac/herres-pawlis

A complete list of the quoted references can be found at http://bit.ly/12aHSmx

Materials

Innovative biopolymer blend

n innovative PLA based blend with improved toughness and durability is close to reaching the market. The material, named Floreon was developed under a TSB funded knowledge transfer partnership between materials scientists at the University of Sheffield and CPD plc, a leading UK distributor of office water cooler bottles. Floreon is intended as a replacement for polyethylene terephthalate (PET) in CPDâ&#x20AC;&#x2122;s 15 litre water bottles, but has also shown promise as a cutting/printing substrate for applications such as key cards and horticultural labels.

A plant pot label made from Floreon

CPDâ&#x20AC;&#x2122;s existing PET bottle

Water cooler bottles present a promising application for this material as they are distributed in a closed loop system. It is intended that the improved durability will make the bottles suitable for reuse, allowing the bottles to go through many cycles of use before further conversion. The team are now exploring the use of reground bottles in extruded sheet applications for cutting and printing, or even reconversion into bottles. When extruded as sheet the material cuts well and is also a good substrate for printing. Floreon sheet items have excellent mechanical performance and feel and the challenge now is to make the material cost competitive. The use of recycled PLA as a base material for Floreon has been trialled with promising results and the aim is to match the price of current materials whilst offering better performance and a range of end of life options. Floreon is unique in comparison with other PLA based blends due to its simplicity and versatility. The patent pending blend uses small quantities of commercially available biodegradable (certified to EN13432) thermoplastics which enhance the mechanical performance of PLA whilst also making it easier to process. The material has passed independent food contact testing with a range of aqueous and fatty food simulants. A further innovation in the works is the use of self-sanitising additives with Floreon. Polycarbonate (PC) bottles can go through hundreds of cycles of reuse, being washed at ~60 Â°C before each refill and using strong detergents and chemicals. The inclusion of additives to prevent biofilm formation would reduce or alleviate this need saving large amounts of energy throughout the bottle life. Initial tests with additives that inhibit microbial growth have shown promising results when combined with Floreon. This could provide an alternative to reusable bottles made from PC, a material associated with health concerns due to the leaching of bisphenol A. The project has also been funded by the REY programme, which is delivered by the low-carbon consultancy CO2Sense and part-funded by the European Regional Development Fund. CO2Sense help businesses and public-sector organisations cut their greenhouse gas emissions and costs, and have accelerated the project with funding to purchase materials and tooling for production trials. www.floreon.com

bioplastics MAGAZINE [03/13] Vol. 8

PLA Recycling

Bioplastics want to be recycled as well EREMA makes sure the loop is closed

Erema T recycling system for the recycling of PLA

lastic is becoming an increasing economic factor as a valuable secondary raw material. The reasons are plain to see. Whereas the production of plastics has risen by 8% per year over the last decade, primary raw material resources are declining dramatically. The fact is that raw material prices are continuing to soar. Increasing importance is being attached to bioplastics from renewable raw materials and high-quality secondary raw materials.

Booming bioplastics trend – but the loop is not closed yet The ever growing ecological awareness in society and the increasing popularity of reusable materials has meant that the demand for bioplastics has risen considerably in recent years and products made of bioplastics have become a booming economic factor. The annual growth rate in Europe, for example, is in the region of 20%, with the share of biobased plastics becoming more and more predominant. According to European Bioplastics some 1.161 million tonnes are currently produced and the forecast for 2016 is over 5 million tonnes (with biobased equivalents of conventional plastics accounting for the major share). In order to be able to close the loop in the bioplastics sector, too, however, you need the appropriate recycling solution. This is currently possible only in the case of production waste in defined loops. Bioplastics in post-consumer waste, on the other hand, are not separated due to the amounts still being too low.

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As the amounts increase, however, so too does the necessity to handle new material flows so existing recycling loops are not jeopardised. The appropriate collecting and sorting systems are becoming increasingly important as a result.

Bioplastics recycling requires expertise Since it was founded in 1983, EREMA (Ansfelden, Austria) has specialised in the development and production of plastic recycling systems and technologies and is regarded as the global market and innovation leader in these sectors. The team of the Austrian group of companies and subsidiaries in the USA and China, plus around 50 local representatives in all five continents provide custom recycling solutions for international customers. The recycling of packaging – made of bioplastics, among other things – is a key field. Erema has already been working on the processing of bioplastics of a wide variety of biopolymer types such as bioPE, bioPET, PLA (fibres, films), PHA, starch-based products, etc. for over ten years – whether it is flat film, blown film or biaxially oriented films and assorted types from a wide range of manufacturers including Mater-Bi® film from Novamont, Ecoflex® film from BASF or Ingeo™ PLA from Natureworks. Erema Marketing Manager Gerold Breuer explains what the recycling of bioplastics entails: “It is important to differentiate between biobased and biodegradable plastics. The characteristics of biobased drop-in types such as bioPET or bioPE are no different to those of conventional plastics based on fossil raw materials – they are merely made from a different raw material. This means that they can be processed with the same parameters. Bioplastics which are both biobased and biodegradable, such as starch-based products or also PLA, require an adapted processing profile in recycling. PLA is very sensitive to moisture, for example, and the shearing forces that arise in the course of processing.“

PLA Recycling EREMA systems already close loops

Rheometry; T=170°C

EREMA T

viscosity

Erema has acquired a wealth of information in the field of bioplastics recycling thanks to over 400 trials in the Erema Customer Centre every year and recycling applications at customers. Bioplastic customers in Europe and the USA are already using Erema recycling systems with success for production waste from defined bioplastic loops. Moisture-sensitive materials such as PLA are carefully cut, homogenised, prewarmed and dried in the patented Erema cutter/compactor. The drying in this process is so efficient that in many cases there is no need for any additional extruder degassing. The warm material which is processed this way is thus melted, filtered and pelletised with minimum shear stress in the extruder. “In many cases PLA material can be recycled with an Erema T system, i.e. without any additional extruder degassing. The drying and treatment in the large cutter/compactor are so efficient and gentle that there is no thermal damage. We know from rheological measurements of recycled materials that the valuable polymer structure is retained and there is no viscosity loss,“ emphasises Gerold Breuer (see diagram).

Viscosity function

Input: PLA mill material

shear rate Research findings confirm that PLA material processed with an EREMA T system, i.e. without additional extruder degassing, can be recycled without viscosity loss

New innovation highlights at K 2013 Erema’s research and development team works continuously on the further development of its technologies in order to drive forward a closing of the loops. The latest innovations from the global market leader will be on show this year at K 2013 (International Trade Fair for Plastics and Rubber, 16 to 23 October 2013, Düsseldorf, Germany). These will include the presentation of a new solution which gives customers additional benefits particularly for temperaturesensitive bio(plastics), too. Gerold Breuer shares with us exclusively what it is all about: “This whole package of technical innovations enables above all optimised material intake so that temperature-sensitive bioplastics such as PLA can also be processed at lower temperatures with high throughput rates.”

Conclusion: (bio)plastic recycling – closing the loop Turning waste plastic, regardless of whether it is bioplastics or not, into high-quality and recognised secondary raw material calls for intensive communication in the entire plastics industry – between raw material suppliers, plastic processors and recyclers. This would result in the development of materials which would take into account their later recyclability at the time they are produced. The way forward is to organise material flows better and optimise the production of plastics in such a way that new, high-quality products with a high recycling content can be achieved. And as Erema says, ‘Closing the loop’ makes sustainability happen. www.erema.at

Bewährt zuverlässige Leistung Vorbildlicher Kundenservice Hohe Innovationskraft Engagiertes und erfahrenes Team

Halle 09, Stand 9B65 16 – 23 October 2013

ww w.gala- europe.de bioplastics MAGAZINE [03/13] Vol. 8

PLA Recycling

PLA recycling via thermal depolymerization by Ramani Narayan Xiangke Shi Daniel Graiver Biobased Materials Research Group Michigan State University

Sample #

Lactide monomer %

Note

93.49

PLA Resin

93.49

PLA Resin

91.79

NatureWorks Ingeo cups

Table 1. Recovery of lactide by catalytic thermal depolymerization

PBAT content

Lactide recovered –no catalyst

Lactide recovered 0.1% SnO2

99.7%

99%

10%

98.7%

99.6%

25%

96.5%

81.6%

50%

80.0%

68.2%

Table 2. Recovery of lactide monomer from PLA-PBAT blends

Figure 3. Laboratory scale recovery of lactide from PLA polymers and blends

Background

LA, poly(lactic acid) is a commercial 100% biobased thermoplastic polymer that has found wide spread industrial applications. It derives its value proposition from having a zero material carbon footprint arising from the short (in balance) sustainable biological carbon cycle. This is different from the process carbon footprint (the carbon and environmental footprint arising from converting the feedstock to product, use, and ultimate disposal, typically covered by LCA methodology [1, 2]. Many issues of bioplastics MAGAZINE have showcased the commercial applications of PLA, and it is the biobased plastic of choice in the market today. The typical end of life option for the PLA product is in industrial composting systems, where it is readily and completely assimilated by the microorganisms present in the compost environment as “food” (completely biodegraded in industrial composting environment) releasing energy that it utilizes for its life processes. A viable end-of-life option for PLA is chemical recycling back to monomer – a virtual cycle of monomer to polymer and back to monomer – a circular biobased economy. PLA can be manufactured by the direct condensation polymerization of lactic acid with concomitant removal of water. However, it is difficult to obtain the high molecular weights necessary for plastics applications because of the low equilibrium constant of lactic acid esterification and the difficulty of water by-product removal in the increasingly viscous reaction mixture.

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PLA Recycling

O O

O CH3

(R,R)-lactide

H3C

CH3

(R,S) or meso-lactide

O CH3

(S,S)-lactide

Figure 1. Stereochemistry of the lactide monomers

Today’s industrial processes are based on the ring opening polymerization of the lactide monomer. First lactic acid is heated under vacuum in a high surface area-to-volume process to obtain PLA oligomers with degree of polymerization between 2 and 25. A metal catalyst is added and the resultant lactide removed by distillation. The PLA system has a rich stereochemical architecture which controls physical and performance properties of the resultant product – the stereoisomers of lactic acid and lactide monomers are shown in Figure 1. The percent meso or D lactide in the L-lactide monomer would affect rate and percent crystallinity and the eventual polymer properties of the polymer product.

Reversible Kinetics model approach for PLA recycling Current approaches to PLA recycle is to hydrolyze it to lactic acid, purify it and then reform into lactide which can then enter into the polymerization step. However, the authors and their workgroup have shown that the polymerization of lactide to PLA follows a reversible kinetic model [3]. “They have used this reversible polymerization to recycle PLA to lactide monomer using catalytic thermal depolymerization with success [4]. The chemistry scheme is shown in Figure 2. Proof of concept was established in a laboratory scale setup with 10-50 gram samples of commercial PLA resin from NatureWorks. Tin(II) 2-ethylhexanoate catalyst was used. Melting occurred at 180-185 °C and the depolymerization reaction started at 185°C.The reaction was carried out under vacuum in a distillation set-up. The lactide distilled over driving the reaction forward. The melting point of lactide is 92-94°C and electric heating tape was used to keep the lactide in the liquid phase after vapor condensed. A trap

Hydrolysis

HO OH Lactic Acid

n tio

H 3C

iza

O H3C

(S) or L-lactic acid

(R) or D-lactic acid

lym po De

O Lactide lym Po

OH Pu Co rific n d at en ion sa tio n

(

HO O

O O

(

Poly (latic acid)

Figure 2 Chemistry of the interconversion between lactic acid, lactide, and poly(lactic acid),

was used to prevent lactide vapor from clogging the vacuum line. The reaction temperature was kept between 185-210°C by using an oil bath. Figure 3 shows the laboratory scale distillation set up with the pale yellow lactide clearly visible in the receiver flask. As can be seen from Table 1 the total yield of lactide was around 94% on a mass basis. Commercial Ingeo™ thermoformed cups were obtained from the marketplace, cut into small squares and added to the reactor vessel, 92% of lactide was recovered on a mass basis. The composition and optical purity of the lactide was established by 1H NMR (Proton Nuclear Magnetic Resonance) (Figure 4). The resonance peak at 1.7 ppm corresponded to meso lactide and the resonance peak at 1.65 ppm corresponded to either LL or SS lactide (Figure 4). Due to the isomeric nature of LL and SS lactide, their resonance peaks are identical in the 1H NMR spectrum. According this analysis, the meso content of this product is 9.5%, very close to the previously reported14 meso content of PLA 3051D (8%). Since PLA is also blended with other polyesters to incorporate biobased content, it was important to establish lactide recovery from such blends. One such blend is a PLA-PBAT (polybutylene adipate-co-terephthalate) reactive blend marketed (e.g.) under the BASF trademark of Ecovio®. Experiments were run with and without tin oxide catalyst. Table 2 shows lactide recovery from blends with varying amount of PBAT resin content. The SnO2 catalyst in the resin did not aid in depolymerization but was processed with the resin. If was found that higher amounts of Ecoflex® (PBAT) in the blended samples prevented recovery of lactide from PLA. PLA samples containing 50 wt% of Ecoflex yielded 80% recovery of available lactide in the samples without resin catalyst and 68% recovery in the samples with resin catalyst. However, the

bioplastics MAGAZINE [03/13] Vol. 8

PLA Recycling 1 1

H3C O

O O D-lactide

H3C

CH3

L-lactide

CH3 1’

1’

H3C O

1.75

2’

CH3

Meso-lactide

2 Solvent

2’ Figure 4 Proton NMR of the recovered lactide from PLA depolymerization

1.70 1.65

1.60

1’

7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 Chemical Shift (ppm)

The depolymerization rate of PLA at constant catalyst concentration is dependent on temperature following the Arrhenius equation The thermogravimetric analysis of samples with 0.6% catalyst at different temperatures are shown in Figure 5. At lower temperatures (160-180), the rate of the reaction was low. After 60 min, the weight loss was less than 50%. In contrast, at 210, the depolymerization reaction resulted in 100% weight loss within only 30 min. In summary, the authors have shown that PLA polymers and their blends can be recycled back to lactide in 95% yields by using a simple catalytic thermal depolymerization process with lactide recovery by distillation. Kinetic modeling and engineering parameters development is in progress to scale to a pilot plant. [1] Ramani Narayan, Biobased & Biodegradable Polymer Materials: Rationale, Drivers, and Technology Exemplars; ACS (an American Chemical Society publication) Symposium Ser. 1114, Chapter 2, pg 13-31, 2012 [2] Ramani Narayan, Carbon footprint of bioplastics using biocarbon content analysis and life cycle assessment, MRS (Materials Research Society) Bulletin, Vol 36 Issue 09, pg. 716 – 721, 201 [3] Witzke, D. R.; Narayan, R.; Kolstad, J. J., Reversible Kinetics and Thermodynamics of the Homopolymerization of l-Lactide with 2-Ethylhexanoic Acid Tin(II) Salt. Macromolecules 1997, 30 (23), 7075-7085. [4] Narayan, R.; Wu, W.-m.; Criddle, C. S., Lactide Production from Thermal Depolymerization of PLA with applications to Production of PLA or other bioproducts. US Patent 13/421780 3/15/2012

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100

Weight percentage [%]

recovery of lactide was unaffected when the amount of Ecoflex was lowered to below 25 wt% in both samples. The addition of resin SnO2 catalyst to the blended samples seemed to lower the recovery of lactide by approximately 10%-15% in blends with greater than 25% Ecoflex. One possible explanation for the decreased lactide recovery in blended samples could be due to the transesterification reaction between PBAT and the lactide oligomers.

80 60 40 20 0

0 10 20 30 40 50 Time [min]

Thermograms (TGA) of PLA depolymerization at different temperatures (from bottom to top: 210, 200, 190, 180, 170, and 160) at 0.6% catalyst concentration.

PLA Recycling

Solvent based PLA recycling by Nathalie Widmann, Tanja Siebert, Andreas MĂ¤urer, Martin Schlummer / Fraunhofer IVV Felix Ecker / University of Applied Sciences Fulda

Fig. 2: no colour changes

n many cases waste containing PLA is currently sorted out as an impurity during the disposal of plastic materials, since low PLA amounts do not yet justify recycling activities. Instead PLA, separated from post-consumer waste, is finally processed into refuse-derived fuel or in waste incineration. With the increasing quantities in recent years the necessity also increases to establish efficient recycling systems for PLA and generate high-quality recyclates guaranteeing a good resource-efficiency. However, recycling of PLA is challenging since in packaging materials PLA is often used as a composite or blend. The main issues are therefore the separation of pure PLA fractions from post-consumer waste and the preservation of its mechanical properties in order to obtain a high-quality recyclate. These issues have not been solved by mechanical state-of-the-art recycling technologies.

The solvent-based CreaSolvÂŽ process was developed by the Fraunhofer Institute for Process Engineering and Packaging IVV in Freising, Germany, in cooperation with the CreaCycle GmbH in Grevenbroich, Germany (owner of the trademark). It represents a future-oriented alternative for the recycling of PLA. The process has been developed for conventional thermoplastics (e.g. PET, ABS, PA, PP, PE and PS) and generates pure and high-quality polymer recyclates from contaminated and heterogeneous waste. The process can be divided into four main steps including solution, cleaning, precipitation (the formation of a solid in a solution during a chemical reaction) and drying of the polymer (Fig. 1).

The CreaSolv formulations used are selective for the respective plastic and non hazardous. Furthermore the process involves precipitation stages for soluble contaminants like degradation products, oligomers or undesired additives. It returns a solution of purified macromolecules where the size and molecular weight were found to comply with virgin material. The major advantage of the CreaSolv process over established mechanical recycling processes is the ability to separate effectively both undissolved foreign polymers and non-plastic materials from the dissolved target plastics. It is therefore particularly suitable for mixed waste and composites. Initial studies on a laboratory scale with PLA allow first statements about solvent selection and selectivity. The PLA solvent was applied to other typical packaging materials (PE, PP, PET and PS) and was confirmed to be selective for PLA. First results show that the molecular weight of PLA can be maintained by specific process control during the dissolution, precipitation and drying stages. Also colour changes of the PLA can be avoided by certain conditions (Fig. 2). Currently, results from laboratory scale experiments are being transferred onto the small scale technical line at the pilot plant of the Fraunhofer Institute in Freising. www.ivv.fraunhofer.de www.creacycle.de

solvent refining

waste

solution

purification

precipitation

drying

product

impurities, contaminants Fig. 1: CreaSolv process (Source CreaCycle)

bioplastics MAGAZINE [03/13] Vol. 8

PLA Recycling

PLA recycling with degassing

he Institute of Plastic Processing (IKV) evaluates the recycling behaviour of PLA. Recycling helps cut raw material consumption and lowers material costs. Additionally, it improves the ecological balance. The different industrially practiced recycling strategies are analysed. A review is given about the processing by means of melt degassing. With the biggest production capacities of all bioplastics Polylactide (PLA) is a promising bio-plastic. However, although many raw material suppliers are starting production lines, the amount of commercially available PLA is still limited [1]. The end-of-life scenario for PLA has rarely been analysed, yet. Mechanical recycling is a reasonable option, but not well known in industry. The aim of this research project is the analysis of the material and process behaviour during mechanical recycling. This knowledge helps converters to improve their production. Production costs and raw material input are reduced. Four research institutes are analysing the recycling of internal PLA waste. Within the project the Flandersâ&#x20AC;&#x2122; PlasticVision (Kortrijk, Belgium) analyses injection moulding while the Institute of Plastics Processing (IKV) focusses on the extrusion process. The chemical analysis of the recycled material and the development of biological chain extenders are done by the Fraunhofer Institute for Structural Durability and System Reliability (LBF), in Darmstadt, Germany. Celabor (Herve, Belgium) characterizes the physical properties of the recycled products and does a Life Cycle Analysis of the different recycling options. In the flat film extrusion process production waste arises mainly from the side cuts. In the thermoforming process punch scrap is produced. Both accounts for almost 40 % of the used raw material. The thermoplastic waste can be melted and reprocessed into a new product. But like every thermoplastic material PLA is exposed to degradation. The hydrolytical degradation is crucial for the processing of PLA. To achieve a sufficient quality certain production steps have to be followed during recycling, e.g. to avoid hydrolytical degradation PLA has to be dried [2]. The material handling of PLA is important. Figure 1 shows the moisture absorption of r-PLA under real storage conditions. After a very strong increase in the beginning the moisture reaches the saturation level at given humidity and temperature. If moisture is present during the plasticization, hydrolysis leads to a very fast degradation. This results in a decrease of the average chain length, which can be described by the molecular weight. A low molecular weight induces insufficient product

bioplastics MAGAZINE [03/13] Vol. 8

properties, e.g. bad mechanical properties and low chemical resistance. Furthermore, the extrusion process is affected. A low molecular weight is followed by a low viscosity and an unstable process. In extreme cases, the process collapses. To prevent hydrolysis an expensive, time and energy consuming pre-drying step has to be conducted. An alternative is the processing by means of a degassing extruder. The degassing allows processing of moist material. By applying a vacuum the moisture is removed during the process and pre-drying is not necessary anymore. Previous analyses have shown that nearly 30 % energy can be saved by using a degassing extruder [3]. Extrusion experiments are done with the IKV equipment on a 60 mm single screw degassing extruder (L=38 D) and a calandar stack. The degassing zone can be closed. In that case the extruder operates as normal extruder. The extrusion line is equipped with a melt pump and a 900 mm flat film die. Additionally, a bypass-rheometer is implemented. Films produced from virgin PLA are used for recycling. A shred mill processes these films to flakes which are subsequently used as r-PLA. Figure 2 shows the melt viscosity depending on the shear rate measured with the bypass-rheometer. It correlates directly with the molecular weight and therefore with the quality of the film. Virgin PLA is processed with a moisture content of less than 250 ppm and without melt degassing. The artificially moistened r-PLA is processed with the specified moisture content. As shown in Figure 2 the melt viscosity drops with increasing PLA moisture. The higher the moisture the stronger is the hydrolysis. At 3200 ppm the viscosity drop is very high. As a result the melt stability is very low and the production of film is not possible anymore. The very strong viscosity drop at low shear rates is a result of the longer dwell times at low shear rates in the rheometer. This shows the very fast reactivity of the hydrolysis. By degassing the polymer melt its moisture is removed during processing. The hydrolytical degradation is lessened. At 750 ppm the viscosity is comparable to the viscosity of virgin PLA. The quality loss is marginal. The degassing of the r-PLA with moisture of 3200 ppm leads not to a sufficient viscosity. One reason is that the capacity of the degassing system is limited. Another reason is that the polymer has to be plasticized before the degassing takes place. Between plasticization and actual degassing, hydrolysis has already started to degrade the polymer chains. At high moisture rates the degradation is too heavy. Hence, the degassing effect is limited.

PLA Recycling

by Ch. Hopmann S. Schippers Institute of Plastics Processing (IKV) at RWTH Aachen University

The higher the moisture content, the lower is the molecular weight. This results from the hydrolysis. By using degassing the molecular weight loss can be reduced. The molecular weight of the 750 ppm r-PLA is nearly as high as the molecular weight of the film made from virgin PLA. Overall, the molecular weight is more stable compared to the viscosity. The trends are the same but the effect on the molecular weight is minor. Apart from the r-PLA with very high moisture content (3200 ppm) the achieved viscosity and the molecular weight are comparable to the values of virgin PLA. The molecular weight loss is little.

4400 4000 3600 3200 2800 2400 2000 1600 1200 800 400 0

PLA moisture [ppm]

The results of the viscosity are confirmed by measurements of the molecular weight of the produced film in Figure 3.

14 time [days]

PLA moisture [ppm]

enviromental humidity [%]

55 50 45 40 35 30 25 20 15 10 5 0

enviromental humidity / temperature

Aachen, Germany

temperature [Â°C]

Figure 1. Moisture absorption under storage conditions

Conclusion 1000

viscosity [Pas]

The material handling of PLA is important for the production process and for the later product quality. PLA shows a strong hygroscopic behaviour. To avoid the expensive pre-drying step the production using melt degassing is recommended. Hydrolysis of the PLA can be reduced as long as the moisture content does not exceed 2000 ppm. At a moisture content higher than 3200 ppm the process and product quality is affected even though degassing is used. In that case a pre-drying step has to be conducted or a degassing system with a higher capacity has to be implemented.

100

virgin PLA moisture 750 ppm 750 ppm 3200 ppm 3200 ppm

degassing no yes no yes

shear rate [s-1]

100

1000

Figure 2. Melt viscosity with and without degassing

Acknowledgment

www.ikv-aachen.de [1] Auras, R.; Lim, L.T.; Selke, S.E.M.; Tsuji, H.: Poly Lactic Acid Synthesis, Structures, Properties, Processing, and Application. Hoboken, New Jersey, USA: John Wiley & Sons Inc., 2010 [2] Brandrup, J.: Recycling and Recovery of Plastics. MĂźnchen, Wien: Carl Hanser Publishing, 1996 [3] Schmitz, T.: Verarbeitung von PET auf einem Einschneckenextruder mit Trichter-und Schmelzeentgasung. RWTH Aachen, Dissertation, 2005

250 weight average molecular weight [kg/mol]

The research project 44EN of the Forschungsvereinigung Kunststoffverarbeitung has been sponsored as part of the Collective Research Networking (Cornet) by the German German Federal Ministry of Economics and Technology (BMWi) due to an enactment of the German Parliament through the AiF. We would like to extend our thanks to all organizations mentioned.

200 150 100 50 0

Moisture [ppm] degassing

virgin

750

3200

yes

Figure 3. Molecular weight with and without degassing

bioplastics MAGAZINE [03/13] Vol. 8

PLA Recycling

Mechanical PLA recycling by Steve Dejonghe Looplife Polymers Hulshout, Belgium

hen PLA was firstly introduced, the main proposal was a shift from fossil resources to renewable ones. But the remarkable versatility of the material also opened new recycling perspectives, further enhancing its environmental profile. Several complementary end-of-life options are therefore possible (ranging from composting to chemical recycling), the most appropriate recycling channel being ultimately determined by the nature of PLA waste. While growing steadily, bioplastics currently account for a marginal share of the global plastic production. Despite the emergence of small PLA post-consumer streams, field experience reveals the difficulties to properly identify recycling channels and shows the challenges to connect streams and potential recycling units. Mid-2000’s, Galactic, a leading actor of the green chemistry, started the first PLA recycling projects in Belgium. Partnering with international key stakeholders, the company was able to build an extensive know-how while acquiring a concrete market experience over the last few years. But to allow further industrial development, Galactic decided end of 2012 to transfer its PLA recycling projects to third parties. The mechanical recycling department has been recently acquired by Devetex, a company active since 1995 in the recycling of off-spec material issued from the textile industry (namely PA66 and PP). As post-consumer streams grew, a dedicated line was also installed in 2005 to handle soiled carpet waste. All know-how and experience acquired by Galactic and Devetex are now combined in one company, LoopLife Polymers, located in Hulshout (Belgium). LoopLife Polymers intends to support market demand for rPLA by proposing a tangible industrial recycling solution for

bioplastics MAGAZINE [03/13] Vol. 8

various compatible waste streams, either post-industrial or post-consumer. For this purpose, the company continues to develop national and international partnerships and is setting a first demo-plant for PLA post-consumer streams (e.g. PLA cups). The philosophy is to turn less established waste streams into useful raw material. LoopLife Polymers and NatureWorks are collaborating to map out regular streams of post-industrial and postconsumer waste which can be considered for mechanical recycling. An effective system to valorize waste is an essential part of the biopolymer value chain optimization. For compatible waste streams, mechanical recycling remains a highly interesting option. With an adequate control of the process, thermal degradation is kept to a minimum and the resulting r-PLA still shows adequate mechanical and thermal properties for a wide range of applications. It also combines the advantages of being both bio-based and recycled, with expected benefits in Life Cycle Assessment studies. Furthermore, LoopLife’s recycling process is optimized to lessen environmental impacts. LoopLife Polymers can therefore be a partner; as an output channel for various PLA waste streams (either Post-industrial, Post-consumer or closed-loop events), with no volume restrictions of compatible streams as a supplier of several high-quality r-PLA grades with constant specifications Such grades are especially interesting for cost-sensitive applications where prime PLA cannot be considered, helping therefore to broaden the use of PLA. These r-PLA grades are well suited for less-demanding, non-food applications. At term, tailor-made grades could be developed to meet specific customer’s requests. www.looplife-polymers.eu

PLA Recycling

Supporting ecological advantages

division of Starlinger & Co GmbH (Vienna, Austria), world market leader in the field of machinery and complete lines for woven plastic packaging production, Starlinger recycling technology provides machinery solutions for the recycling and refining of a wide scope of plastics such as PE, PP, PLA, PA, PS, BOPP and PET. Starlinger recycling technology has focused on production waste: although companies emphasize the concept of zero-waste, production waste cannot be avoided completely. Mechanical recycling is the answer as use of rPLA can be up to 100 %.

Equipped with a heavy-duty single-shaft cutter arranged parallel to the extruder, the recostar universal enables also the processing of film and additionally of hard-togrind materials such as containers, fibres and start-up lumps. The hydraulic pusher in the single shaft cutter presses the material against a water-cooled rotating shaft and thus provides efficient crushing. The new feeding system into the extruder accounts for increased operational reliability, simplified operation, and lower energy consumption and higher output at the same time. Five extruder sizes from 150 – 1,300kg/h are available.

Decisive for the quality of the end product: Input material and recycling process

Vacuum treatment, fine filtration and pelletising

PLA is now used in many applications, such as film for packaging, containers for juices, filaments for fabric, etc. New technologies allow the recycling of PLA in a way that high-quality re-granulate becomes a cost-saving alternative to virgin resin. To ensure the production of high value regranulate – which is the requirement for improving cost efficiency and stability of the production process – an analysis of the input material and the right choice of equipment is paramount. Starlinger recycling technology offers two suitable systems for the recycling of PLA production scrap: recoSTAR basic and recoSTAR universal.

It’s all in the melt: To ensure high-quality regranulate although PLA is hygroscopic, both recycling systems can be equipped with an extruder vacuum unit in order to extract volatile contaminants and reduce viscosity loss in the melt. A variety of melt filtration systems ensure clean, high-grade melt: melt filters with and without backflushing, and power backflush filters are the most common. The choice of filter type and size depends on the type and amount of contaminants (e.g. paper) and required fineness (50 µm positively tested). Customers can choose water ring pelletizing, manual and automatic strand pelletising or underwater pelletising. MT

Technology principles

www.recycling.starlinger.com

The recostar basic uses an agglomerator for cutting the material by means of knives on a rotating disc at the bottom, suitable for film and pre-cut material. This frictional process heats and dries the mixed material, densifies it and brings it close to the melting point before it is fed into the extruder. Six extruder sizes from 150 – 2,200 kg/h are available.

bioplastics MAGAZINE [03/13] Vol. 8

PLA Recycling

Linear polymer

Better-than-virgin recycled PLA

I Chain extended polymer (PLA + chain extender by reactive extrusion) Ex: CESA-Extend, Joncryl, other epoxides

Hyperbranched PLA (PLA + IFS Proprietary Chemistry by Reactive Extrusion) Top: PLA extrudate from a cast film process at 180Â°C, bottom: hyperbranched PLA,

nterfacial Solutions LLC (River Falls, Wisconsin, USA) has developed proprietary processing technology that converts scrap PLA, possessing inferior properties, into a recycled PLA resin with properties that exceed those of virgin PLA. To do so, Interfacial Solutions utilizes a novel reactive extrusion process and chemistry to hyperbranch PLA polymer within a continuous extrusion process. Interfacial Solutions has shown that hyperbranching dramatically increases the molecular weight of the polymer while simultaneously creating many random branching sites along the backbone of PLA, creating a unique rheology during melt processing. The result is an improved PLA resin with superior melt strength and mechanical properties to virgin PLA. The hyperbranched recycled PLA resins are particularly suited for profile extrusion applications in durables markets. PLA itself is a linear polymer with low melt viscosity, and as a consequence, does not exhibit substantial melt strength during processing. Branching of PLA through chain extension chemistries has been shown to improve melt strength, however, these chemistries work only on the chain ends of the polymer. Hyperbranching produces a unique molecular architecture from many random long and short chain branching events. This molecular architecture allows for improved melt processing compared to both linear and conventional chain extension by providing substantial melt strength enhancement, but at lower shear viscosity in the melt [1]. In other words, profile control of the extrudate can be dramatically enhanced without large increases in die pressure and torque on extrusion equipment. An additional benefit to hyperbranching is that the increased molecular weight of the polymer makes PLA less susceptible to processing variations caused by moisture. It is well known that moisture in PLA resin during processing creates process instabilities due to hydrolysis of the PLA polymer at elevated temperature. The significantly greater molecular weight and branched structure of hyperbranched PLA makes for a lesser impact of hydrolysis. From the perspective of recycling PLA through the reactive extrusion process, the incoming scrap PLA feedstocks do not require drying to the levels recommended by users of prime PLA grades. It is possible to counteract the hydrolysis caused by moisture with adjustments to the chemistry used in the reactive extrusion process, effectively allowing repeated melt processing without drying. Interfacial Solutionsâ&#x20AC;&#x2122; proprietary technology was originally developed to enhance the performance of compounds produced from virgin. Through a prestigious grant from the Na-

bioplastics MAGAZINE [03/13] Vol. 8

PLA Recycling

by Adam R. Pawloski, Brandon J. Cernohous Gregg S. Bennett, Jeff J. Cernohous Interfacial Solutions / River Falls, Wisconsin, USA

tional Science Foundations Small Business Innovation Research (SBIR) program (Grant No. IIP-1215292), Interfacial Solutions expanded the technology to make it amenable to recycling processes by converting low quality PLA scrap into hyperbranched, recycled PLA resins of greatly improved mechanical and rheological properties. As demonstrated by the data in Table 1, even very poor quality scrap can be effectively converted into hyperbranched resins with better-than-virgin properties. The technology works effectively on both post-industrial and post-consumer scrap, allowing for multiple options of source materials. Products based on hyperbracnehd, recycled PLA are available for purchase under the deTerra® product line. www.interfacialsolutions.com [1] Pawloski, A. R. et al., “Recycled PLA Feedstocks by Hyperbranching,” Global Plastics Environmental Conference (GPEC), New Orleans, 2013.

Examples of molded and extruded articles made from deTerra® biobased polymer Resin

MFI (g/10min, Mw Flexural 190°C, 2.16 kg) (kg/mol) Strength (kpsi)

Virgin PLA (NatureWorks 2003D)

6.0

220

155

Hyperbranched, virgin PLA (XP759)

2.7

425

156

Prime Grade Post-industrial PLA

11.8

145

153

Low level hyperbranching

6.8

142

153

Intermediate level hyperbranching

3.2

464

155

High level hyperbranching

1.6

470

155

Low Grade Post-Industrial PLA

420.0

108

Low level hyperbranching

285.0

125

Intermediate level hyperbranching

290.0

145

122

High level hyperbranching

130.0

300

135

Post-Consumer PLA

5.0

187

145

Low level hyperbranching

0.8

398

141

Intermediate level hyperbranching

0.3

518

145

High level hyperbranching

0.0

---

149

Table 1. MFI, Molecular Weight, and Flexural Strength of Hyperbranched, Recycled PLA Resins

‘Basics‘ book on bioplastics This book, created and published by Polymedia Publisher, maker of bioplastics is available in English and German language.

MAGAZINE

The book is intended to offer a rapid and uncomplicated introduction into the subject of bioplastics, and is aimed at all interested readers, in particular those who have not yet had the opportunity to dig deeply into the subject, such as students or those just joining this industry, and lay readers. It gives an introduction to plastics and bioplastics, explains which renewable resources can be used to produce bioplastics, what types of bioplastic exist, and which ones are already on the market. Further aspects, such as market development, the agricultural land required, and waste disposal, are also examined. An extensive index allows the reader to find specific aspects quickly, and is complemented by a comprehensive literature list and a guide to sources of additional information on the Internet. The author Michael Thielen is editor and publisher bioplastics MAGAZINE. He is a qualified machinery design engineer with a degree in plastics technology from the RWTH University in Aachen. He has written several books on the subject of blowmoulding technology and disseminated his knowledge of plastics in numerous presentations, seminars, guest lectures and teaching assignments.

110 pages full color, paperback ISBN 978-3-9814981-1-0: Bioplastics ISBN 978-3-9814981-0-3: Biokunststoffe

Order now for € 18.65 or US-$ 25.00 (+ VAT where applicable, plus shipping and handling, ask for details) order at www.bioplasticsmagazine.de/books, by phone +49 2161 6884463 or by e-mail books@bioplasticsmagazine.com

Or subscribe and get it as a free gift (see page 69 for details, outside German y only)

bioplastics MAGAZINE [03/13] Vol. 8

PLA Recycling

Chemically recycling post-consumer PLA

PLA, turning waste back into lactic acid from which new, non-food products again could be made.

research project at the University of Wisconsin-Stevens Point over the past two years has instituted what is believed to be the first concerted effort in the USA to collect and recycle post-consumer PLA.

A secondary goal was to test awareness on campus about PLA and its sustainability attributes, and to learn to what degree a publicity campaign could influence knowledge about PLA and improve recycling success. As part of the public relations aspect, Kratz hired several assistants to create a campaign. The campaign was called the FRESH project, for Focused Research Effort for Sustainable Habits. It is believed to be the first such recycling campaign at any university in the U.S. and the first attempt at recycling post-consumer PLA.

Today, PLA is technically recyclable but infrastructure is not in place for recycling post-consumer PLA. The Wisconsin Institute for Sustainable Technology (WIST) at UW-Stevens Point inaugurated a plan to create the recycling infrastructure on a small scale to determine the practical feasibility of chemical recycling of post-consumer PLA. UW-Stevens Point dining services began buying food service ware of PLA plastic in 2009 as an initiative in sustainability. However, no system for collecting and composting or recycling the material was in place at the university. In fact, the switch to PLA from the polystyrene foam products the university had been using had been intended in part as a way to kick-start a compostability service on campus. But that didn’t happen, either.

Publicity included informational kiosks and displays, surveys, social media and poster campaigns to educate the campus community about PLA environmental benefits and end-of-useful-life options for the bioplastics. Additional recycling containers specifically labeled for PLA food service ware disposal were placed in dining areas for source separation of the PLA waste where consumers were most likely to be using and disposing of the items.

The FRESH Project

FRESH project student employees collected material from the recycling bins and sorted the material to separate PLA from other materials. Although the bins were clearly labeled, there was inevitably other material deposited. The postconsumer PLA was washed, dried and stored before being transported to a chemicals’ re-processor elsewhere in the state that chemically recycles post-industrial and off-grade PLA resin, but had not recycled post-consumer PLA.

In an effort to more fully take advantage of the PLA attributes, WIST created a research project to collect and recycle post-consumer PLA. A graduate student in soil and waste resources, Waneta Kratz, was recruited to take on the project in conjunction with her graduate research. The project had several aspects. The primary research goal was to determine how much processing – rinsing and washing – was required in order to successfully recycle post-consumer

Level

Time, min

Temp, °C

NaOH, wt %

Surfactant, wt %

Low

0.1

High1

0.3

Table 1. Washing parameters for post-consumer polylactic acid (PLA) waste. Low-level indicates FRESH wash method only; high-level indicates adapted industrial PET recycling wash [1].

bioplastics MAGAZINE [03/13] Vol. 8

PLA Recycling

by Paul Fowler Waneta Kratz Ron Tschida Wisconsin Institute for Sustainable Technology University of Wisconsin-Stevens Point Stevens Point, Wisconsin, USA

Chemical recycling analysis Recycling post-consumer PLA presents an additional problem in that it is contaminated by food. Prior to the WIST research no studies had been done nor any procedures established in the USA for cleaning post-consumer PLA for chemical recycling. The WIST project designed two different rinsing protocols to test whether a light rinse or more intensive washing was required for effective chemical recycling. The procedure for an intensive wash was adapted from a standard washing procedure [1] for post-consumer PET containers such as beverage bottles. A low-level treatment was designed by Kratz for the FRESH project. (See washing parameters summarized in Table 1, adapted from Kratz thesis, unpublished, used with permission.) Chemical recycling of PLA is done by hydrolysis, with pressure and heat added to speed the process. To test the rinse processing methods, laboratory hydrolysis in sealed flasks was performed on PLA that had received a high-level treatment, PLA receiving a low-level treatment, and on preconsumer PLA as a control. The PLA products tested were clear plastic cups made from NatureWorks Ingeoâ&#x201E;˘.

Total acid recovery in all treatments and controls exceeded the client specification and ranged from 89.5 to 96.0% for total acid (see Table 2, adapted from Kratz thesis, unpublished, used with permission). The difference in acid recovery was insignificant between samples receiving a low-level treatment and those receiving the more intensive treatment. The results indicated that even a low level rinse of post-consumer PLA is adequate for chemical recycling. The intensive wash procedures used for PET may not be necessary to chemically recycle postconsumer PLA. Further research is needed on this topic, and experiments on a larger scale would be useful toward developing practical infrastructure. Meanwhile the FRESH project is ongoing at UW-Stevens Point. [1] Chariyachotilert, C., Selke, S., Auras, R.A., and Joshi, S. 2012. Assessment of the properties of poly(L-lactic Acid) sheets produced with differing amounts of post-consumer recycled poly(L-lactic Acid). Journal of Plastic Film and Sheeting 28: 314â&#x20AC;&#x201C;335.

Recovery through chemical recycling was evaluated in terms of the amount of free acid and total acid in the hydrolyzed lactic acid product. There is currently no industry standard published for successful lactic acid recovery. However, a potential client had specified that recovered material should contain 68.5-74.5% free acid and 80-91% total acid. WIST used those numbers for comparison purposes.

Treatment Sample Starting mass (g) Recovery (g) Recovery % Recovery Average % Preconsumer PLA Low-level

High-level1

1 2 3 4 5 6 7 8 9

113.59 113.60 112.24 113.60 113.60 113.60 113.60 113.62 113.62

108.57 109.42 106.91 103.13 105.10 105.32 101.84 104.19 102.61

95.58 96.32 95.25 90.79 92.52 92.71 89.64 91.71 90.31

95.71

92.01

90.55

Table 2. Recovery of lactic acid product from chemical recycling of polylactic acid (PLA) cups. Lowlevel indicates FRESH wash only; high-level indicates adapted industrial PET recycling wash [1]

bioplastics MAGAZINE [03/13] Vol. 8

PLA Recycling

Recycling ‘hands on‘ The Perpetual Plastic Project with live, interactive demonstration

he sustainability and feasibility of various end-of-life options for bioplastics remains a hot discussion topic. The actual application, of course, has a strong influence on which end-of-life option could be the most sustainable. For Purac, Gorinchem, The Netherlands, recycling is the preferred option where possible. This ensures that valuable raw materials remain in the value chain for reuse in future applications. As a result, Purac – a leading company in lactic acid based bioplastics – has sponsored the Perpetual Plastic Project to highlight how easily PLA bioplastic can be recycled. PLA drinking cups were provided by Purac; intended for use at events where people can immediately recycle them into new products after use. The project is designed to educate people on the recyclability of bioplastic, in order to close the loop and promote a circular, biobased economy for future generations.

The Perpetual Plastic Project on tour

The Perpetual Plastic Project has successfully created a do-it-yourself’, interactive machine, which provides users with a small-scale demonstration of how easily PLA can be recycled: following the steps of cleaning, drying, shredding, melting and extrusion, before finally being remade into a new article. In this case, a 3D printer was used to create jewelry and small toys from the used PLA cups. The machine has toured the Netherlands at numerous events, including the Dutch Design Week in Eindhoven, the Science Center NEMO in Amsterdam and the National Sustainability Congress in Nieuwegein. The Perpetual Plastic Project is an initiative created by former TU Delft students. Purac, together with GroenBeker, provided the PLA bioplastic drinking cups which accompanied the machine. François de Bie, Marketing Director Purac Bioplastics, is pleased with the project: “This initiative demonstrates in a tangible, understandable way just how easily PLA can be recycled. Although PLA is still a relatively new material to the plastics industry, it promises to become widely implemented throughout a broad range of applications. It is therefore vital that we already start to think about how best to recycle these valuable materials. Thanks to the Perpetual Plastics Project, we can show people at events and festivals what can ultimately be achieved on a much larger scale’. Purac has created a short video to highlight the project and the recyclability of PLA. www.purac.com/bioplastics.

Info: See http://bit.ly/18SnQiM (or scan the QR-code) to view the video-clip.

bioplastics MAGAZINE [03/13] Vol. 8

PLA Recycling

Pelletizing and crystallizing of PLA â&#x20AC;&#x201C; an analogy to PET?!

s PLA finds more and more applications it gives rise to the question of which are the most appropriate technologies for processing. Because of the low glass transition temperature of PLA the crystallization of the plastics may play a decisive role in identifying further processing, depending on the exact material parameters and processing tasks. The strong analogies of PLA and PET concerning water absorption and crystallization behaviour suggest that processes which can be successfully used for the crystallization of PET are also suitable for the processing of PLA. Meanwhile there are some very different methods for the crystallization of PET as virgin and recycled material. An essentially energy-efficient method is the so-called inline crystallization in combination with an underwater pelletizing system, as introduced by BKG Bruckmann & Kreyenborg Granuliertechnik GmbH of MĂźnster, Germany.

Complete BKG-KREYENBORG discharge unit consisting of melt pump, screen changer, polymer valve and underwater pelletizing system

With the processing of thermoplastics underwater pelletizing systems play an increasingly important role and may slowly replace classic strand pelletizing systems. The spherical pellets, obtained by using a die-face, are the starting point for the following inline crystallization. The cut pellets are transported in extremely hot process water to the centrifugal dryer, in which they are separated from the water. The amorphous pellets exit the dryer at a very high temperature and fall onto a special vibrating conveyor. Under permanent motion, which prevents a sticking together of the hot pellets, the PET crystallizes automatically from inside to outside solely due to the residual heat. Unlike other processes, no additional energy has to be supplied from outside. With the processing of PET a crystallization degree of about 45 % may be achieved. Additionally the pellets do have such a high temperature that further heating for downstream processes is often not necessary.

Microscopic picture of PLA resin, which was crystallized with the CrystallCut system of BKG

The analogy of PET and PLA is the starting point for a use of this extremely energy-efficient process for the processing of PLA as virgin and recycled material. A direct use depends on the exact parameters and requires an exact adaptation of the process. As soon as this procedure is successfully identified a cost-efficient and energy-saving method for the crystallization is available for PLA processors. Thus the attraction of the forward looking plastic, PLA, is further increased. MT www.bkg.de

bioplastics MAGAZINE [03/13] Vol. 8

Portrait

10 years FKuR

he bioplastics compounding company FKuR from Willich, Germany, celebrates its 10th anniversary this June. bioplastics MAGAZINE spoke with co-founder and CEO Edmund Dolfen. bM: Edmund – first of all happy birthday for the 10th anniversary of your company. Could you briefly tell us about the origins of FKuR? Dolfen: The roots were in our care for the environment, especially in recycling. FKuR used to be an abbreviation for Forschungsinstitut Kunststoff und Recycling established in 1992. When founding the FKuR Kunststoff GmbH in 2003 we were convinced that nature itself is the best recycler. That was the basis for the development of biodegradable plastics. bM: And today? Dolfen: Biodegradable and compostable plastics are still our main markets including applications where the natural degradation in nature is included in products such as mulch films. In these compounds we try to include as much biobased material as possible. So, our second biggest field of activity are materials made from renewable resources. The reasons are obvious: fossil resources are finite and become more and more expensive and they burden the climate with additional CO2. We compound and distribute, for example, Green PE by Braskem made from sugar cane which is grown in freely available areas in the South of Brazil and does not affect the deforestation of the amazon rainforest. bM: What is your secret of success? Dolfen: We are technically inventive and we have strong development partners such as Fraunhofer UMSICHT. We have a huge number of external development agreements which result in a broad portfolio of products, such as for film blowing, extrusion, injection moulding and thermoforming. bM: In recent years the bioplastics sector has grown significantly and more and more players appear on the scene. What differentiates FKuR from other suppliers? Dolfen: One advantage is our company philosophy. We constantly try to perfect our consulting and development service, from the first idea to a marketable product. There are so many different new resins available. We develop blends with optimized processability and properties.

bM: Which are the most pleasant experiences in your company history? Dolfen: I’d say in the first instance the people around us, i.e. our shareholders who all are active in the company, the employees, 40 by now, who all participate in our success, and most importantly the partners who accompany us, i.e. the suppliers, customers and many development partners. This pleasant surrounding allows us to grow smoothly and efficiently. bM: What ideas are behind the latest agreements you have made? Dolfen: We are seeking renewable solutions for all important applications. The name FKuR represents the task: When you are looking for a biobased solution, FKuR offers a suitable resin, either our own compounds or products that we distribute. Our driver is supporting the customer with his new products and markets. bM: What are your future targets? Dolfen: Beside continuing expansion with biodegradable products the biggest challenge for the future is to realize as many renewably sourced materials as possible. We not only owe this to our suffering environment but also to future generations. And new biobased materials are standing by. bM: For example? Dolfen: We will announce them in due course. The most interesting candidates are biobased PET and biobased PA. bM: How do you manage these sales challenges? Dolfen: We have also started to focus on direct customer sales, which is a real challenge for our engineers. So, we are integrating more native speakers, who can cope with the multiple European mentalities. bM: May I ask a personal question? Dolfen: Please go ahead! bM: You are now 72 years old. How long will this go on? Are you considering retirement? Dolfen: I was lucky to gather a lot of entrepreneurial knowledge and experience during my career. I’d like to pass them on and we are developing them further within our young team. The management in FKuR is well structured – so I could retire from daily management and concentrate on strategic moves and co-operations. bM: Is there a world other than FKuR? Dolfen: It’s a question of balance and continuity. I enjoy the job and the responsibility. So, it becomes a question of what is essential for you during your unique visit on this earth and what gives you the perception of happiness. For the sake of the balance I am preparing for more time for other essentials in life, for instance hobbies like arts and painting. I like to paint portraits in oils, since I love people and faces. Each one represents an individual history and exciting character which are reflected in his face. bM: Thank you very much.

bioplastics MAGAZINE [03/13] Vol. 8

Opinion

Biobased: Lose the hyphen by Ron Buckhalt U.S. Department for Agriculture (USDA)

ook at this issue of bioplastics Magazine and you will see nearly all things bio are not hyphenated. They are one single word, biobased, biodegradable, bioplastics, biopolymer, biorefineries, and biomass. Even the name of the publication, bioplastics Magazine, is not hyphenated. Look at any U.S. Federal government document and you will see most things bio, including biobased, are not hyphenated. This was not always the case. Many of these words were hyphenated when first used because they were new in use. So while much progress has been made, we continue to see biobased spelled with and without a hyphen. As one who was working with biobased industrial products in the early 1980’s directing marketing and communications campaigns I had to constantly fight my computer which kept correcting to bio-based. It was frustrating until I added to the term biobased to my computer’s accepted dictionary. I have even added biobased some years ago to the memory of the new machine on which I am now working to make sure it is accepted. Of course, the mid-80’s was also the same time automatic spell check would change biobased to beefalo. I actually saw one published document in the 80’s which the author did not double check, but left it to spell check to take care of, that had beefalo throughout. Go figure. At that point I promised myself that if I did nothing else in life I would do what I could to make sure biobased became the accepted spelling. So when we worked on ”Greening the Government” Federal executive orders in the 80’s and legislation creating our BioPreferred program in 2001-2002, we sought to standardize the term to biobased in all Federal government documents. Biobased is the way it is spelled in the 2002 and 2008 U.S. Farm Bills that first created our BioPreferred program and then amended it. Our intent was to make biobased a noun by usage, not just an adjective always modifying product. New words are created everyday and the dictionaries eventually catch up. Words and terms like bucket list, cloud computing, energy drink, man cave, and audio dub were recently added. They have been around for a while. In the

case of biobased that has not yet happened. Biobased is not in Webster, not even bio-based. Yet Wikipedia has it listed as biobased. The name of our program, BioPreferred, was not in the Farm Bill legislation. It is a made-up word for marketing purposes to signify the Federal purchasing preference for products made from bio feed stocks as well as the many advantages to consumers and the environment. You won’t find BioPreferred in a “proper” dictionary. Even Wikipedia just points to the BioPreferred web site and when you do a computer search for BioPreferred our program name pops up. We hold a patent on the term by the way. In the large scheme of things whether we hyphenate biobased or not is probably no big deal. But there are those of us who believe biobased is a movement, not an adjective, and that is why we have dedicated most of our working career to advancing the cause and we want to spell it biobased and we want to see it in Webster.

bioplastics MAGAZINE [03/13] Vol. 8

Report

Bioplastics for food packaging

Pouches

% O2

1,5 1 0,5 0

0 10 20 30 40 Day Tray

% O2

1,5

Characterization of biobased materials

1 0,5 0

two year research project at Ghent University (Department of Food Safety and Food Quality, Ghent, Belgium) has shown that bioplastics have a great potential as a packaging material for various types of food products (short, medium and long shelf life), including packaging under modified atmosphere (MAP). This research project, initiated by Pack4Food and funded by the Agency for Science and Technology (IWT, Brussels, Belgium), was led by Prof. Peter Ragaert and performed in close collaboration with different research institutes (Ghent University, University college Ghent, Packaging Centre, Belgian Packaging Institute and Flandersâ&#x20AC;&#x2122; Plastic Vision) and 22 companies.

0 10 20 30 40 Day

Fig 2: O2 concentration during the shelf life of ham sausage packed in pouches made of Natureflex type 1 , Natureflex type 2 and in the reference package or packed in a PLA tray with a Paper/Alox/PLA topfilm , a Natureflex type 1/PLA topfilm and in the reference package .

The project started with the characterization of multilayered biobased materials that were found on the market or that were laminated especially for this project. Different parameters important for food packaging materials, like barrier properties (Table 1), seal properties and mechanical properties, were collected (from technical sheet or by measurements at the Packaging Centre). The large variation in film characteristics of the different tested materials shows that for various types of food products a suitable biobased packaging material can be found.

Storage tests Food product Short shelf life (storage under cooling)

Medium shelf life (storage under cooling)

Long shelf life (storage at room temperature)

Selected films

Tomatoes

PLA tray + Multilayer PLA

Rumpsteak

PLA tray + Natureflex type 1/PLA

Ham sausage Filet de Saxe

Natureflex type 1 Natureflex type 2 PLA tray + Natureflex type 1/PLA

Ham sausage

PLA tray + Paper/AlOx/PLA

French fries Grated cheese

Natureflex type 1 Natureflex type 2

Potato flakes

Skalax (Xylophane) Natureflex type 2

Rice cakes Tortillachips

Cellophane /M/PLA Natureflex type 1 Natureflex type 2

Speculoos

Cellophane /M/PLA Natureflex type 3 Natureflex type 4

Table 2: Overview selected food products and films

bioplastics MAGAZINE [03/13] Vol. 8

Based on the characterization, different multilayered bioplastics were selected to pack different food products (short, medium and long shelf life) (Table 2). Several food products were packaged under modified atmosphere (mostly a mixture of N2 and CO2) which is a commonly used preservation technique in the food industry. The food products were analyzed for microbiological, chemical and sensorial parameters at certain times during their shelf life and the results were each time compared with their evolution in the conventionally packaged food products. Some examples of tested packages are shown in Figure 1a and 1b. The results were mainly positive for the short and medium shelf life products, which were all MAP packed, except for the tomatoes, and stored at 4Â°C. All tested multilayered bioplastics showed sufficient barrier against O2 and CO2 to maintain the shelf life of the tested food products, as shown for ham sausage in Figure 2. For most other parameters, no differences between the biobased packages and the conventional packages were observed. Only for rumpsteak and ham sausage packed in trays, more loss in red or pink color was observed in the bioplastics packaging by the color measurements and these results were confirmed during the sensorial evaluations (performed at the

Report by Material

Nanou Peelman Peter Ragaert Ghent University Faculty of Bioscience Engineering Ghent, Belgium

respective food companies). This difference in color could be caused by different UV-transparency properties of the materials. For the dry, long shelf life products, maintaining crispness is essential. Moisture barrier is very important for these food products, which were packed under air, except for the potato flakes, which were MAP packed, and stored at room temperature. Tortillachips and rice cakes maintained their crispness when they were packed in the biobased packaging during 6 or 12 months. Also no different lipid oxidation occurred compared to the conventional packaging. For potato flakes, no good sealed packages could be made from the Xylan based material (due to food product contamination on the sealing zone during filling), but the Natureflex™ film showed similar barrier properties as the conventional film. Furthermore, no difference in parameters was observed between both films. Because of the small packages, dry biscuits were immediately packed at the company itself. Small holes and micro leaks in the seal (due to the thickness of the film) caused to much moisture uptake by dry biscuits packed in the Natureflex type 3 film. Less moisture uptake was observed in the Natureflex type 4 film, but still the moisture barrier was insufficient to keep the biscuits crisp during the entire shelf life of 30 weeks.

Printability and migration tests The Natureflex type 1 film (Fig. 3) was printed in the framework of a collaboration between Lima (organic food products) and Be_Natural (packaging consultant sustainable packaging). This packaging went commercial in 2012. Besides, a multilayer PLA film was printed at Vitra NV during the research project. The film could be printed without any problem and further testing showed good adhesion of the inks on the film surface. The PLA film seemed however receptive to solvents, which should be solved by applying other types of inks or adjusting the print design (no full surfaces). Global migration tests (10% and 95% ethanol) showed that all the tested multilayered biobased films did not exceed the limit of 10 mg/dm2.

Natureflex type 1 Natureflex type 2

H2O

(cm³/m ·d) 23°C - 75% RH

(g/m2·d) 38°C – 90% RH

9.9

10.1

3.4

5.0

Ecoflex+Ecovio/Ecovio/Ecoflex+Ecovio

815.0

216.4

Metallised PLA

25.4

2.3

Cellophane /Metal/PLA

9.1

9.7

Paper/AlOx/PLA

45.7

6.0

Bioska (multilayer PLA)

617.6

275.1

Natureflex type 1/PLA

11.01

11.3

PHB/Ecoflex

142.1

80.6

Xylophane A (coated on paper)

3.7

24.3

PLA tray (Ingeo)

46.8

3.8

Table 1. Barrier properties of multilayered biobased plastics

In conclusion, this collaborative research project shows promising results for packing different food products in bioplastics without compromising the desired shelf-life. This also includes applications for MAP packaging. Moreover, some of the tested materials are already in use today. Examples are given in Fig. 3 (rice packaging - company Lima) and Fig. 4 (sliced meat packaging – company Ter Beke). Further attention however needs to be given to bioplastics materials for certain moisture sensitive food products in need of a high moisture barrier. Besides, the participating companies in the project mentioned issues such as current price and waste management options as important parameters in the decision and implementation process of companies whether or not to add bioplastics in their product portfolio. www.foodscience.UGent.be www.Pack4Food.be www.iwt.be

Left Figure 1a. Ham sausage in PLA tray + Natureflex type 1-PLA Right Figure 3. Rice packaging from company Lima (www.limafood.com)

Case studies at food companies Several bioplastics were selected to be tested in production environment at different participating companies in the project. On the vertical flow pack machines, only easily solvable problems were encountered (e.g. optimizing time-temperature settings) and good sealed packages could be made. On the horizontal flow pack machines, it was also possible to make sealed pouches, but some of the films seemed too brittle to be filled with a large amount of product.

Figure 1b. Tortillachips packed in reference (l) - natureflex type 2 (m) - natureflex type 1 (r)

Figure 4. Sliced meat packaging from company Ter Beke (www.terbeke.com)

bioplastics MAGAZINE [03/13] Vol. 8

Basics

Succinic acid by Michael Thielen

s industry transforms from petro-based to environmentally sustainable materials, succinic acid is emerging as one of the most competitive of the new bio-based chemicals [1]. Succinic acid (IUPAC name Butanedioic acid, other names are amber acid or ethane-1,2-dicarboxylic acid) is a colorless, crystalline, aliphatic dicarboxylic acid with a chemical formula C4H6O4 and structural formula HOOC-(CH2)2-COOH [2] Succinic acid is a platform or bulk chemical with global production rate of between 30,000 and 50,000 tonnes per year. The market is expected to grow at a compound annual growth rate of 18.7% from 2011 to 2016. It can be used directly or as intermediate for a large number of applications such as for plastics, paints, food additives and other industrial and consumer products. Until recently, succinic acid was produced mainly by chemical processes from petrochemical feedstocks, such as butane or benzene via the conversion of maleic anhydride to succinic anhydride followed by hydrolysis. Alternative routes include the oxidation of 1,4-butanediol and the carbonylation of ethylene glycol [3, 4, 5].

Fig. 1: (source [2])

But succinic acid can also be produced by fermenting carbohydrate or glycerol using engineered bacteria or yeast. Current commercial routes are based on proprietary E. Coli and yeast strains, developed by BioAmber and Reverdia respectively. BioAmber are also developing a next generation process based on yeast fermentation, developed by Cargill [4].

O HO

OH O

The downstream processing of succinic acid post fermentation is critical to the cost of production. The need to control (buffer) the pH during fermentation results in succinate salt formation which then needs to be ‘cracked’ to recover the free succinic acid. The use of low pH tolerant yeast removes the need for buffering and therefore simplifies downstream processing reducing costs [4].

Bio-succinic acid Different companies are active in field of biobased succinic acid [4]: Fig. 3: thermoformed clamshells made of PBS (GS Pla, source Mitsubishi Chemical)

bioplastics MAGAZINE [03/13] Vol. 8

BioAmber, a renewable chemicals company based in Minneapolis, USA has been producing and supplying biosuccinic acid at commercial scale out of a plant in Pomacle, France, since 2010. This plant was built in partnership with Agro Industrie Recherches et Developpements (ARD) of France and has a capacity of 3,000 tonnes. BioAmber’s product is marketed under the brand name BioAmber Bio-SA™ The comoany has been working with Cargill on a second-generation organism to produce BioAmber BioSA, based on Cargill’s proprietary SBA yeast, which builds on decades of Cargill experience in the field. BioAmber is building an industrial scale plant for bio-succinic acid and bio-1,4 butanediol, with an initial projected capacity of 30,000 tonnes of Bio-SA and 50,000 tonnes of bio-1,4 butanediol in Sarnia, Canada. The SBA yeast enables lower capital and operating costs, as well as a simplified purification process, which drives down facility and production costs to ensure

Basics

Fig. 2: Examples for of typical polyurethane applications including the renewable content due to the use of bio-based succinic acid (Source Reverdia)

the lowest cost option for bio-succinic acid. BioAmber Bio-SA produced using the SBA yeast can metabolise non-agricultural feedstocks and has a carbon neutral Life Cycle Analysis (LCA) from field-to-gate, effectively reducing greenhouse gas emissions by 99.4% and providing energy savings of 56.3% compared to petroleum succinic acid. [6].

Reverdia (a joint venture between DSM and Roquette Frères) is employing a low-pH yeast technology to produce their product which is branded Biosuccinium™. The proprietary technology is less complex, direct and has several distinct advantages over bacteria-mediated conversion technologies, but one of them in particular stands out: the Reverdia process converts feedstock directly to acid. Bacteria-based processes are indirect, and therefore require extra chemical processing, additional equipment and additional energy to convert intermediate salts into succinic acid [7]. Reverdia recently opened the worlds first commercial-scale bio-based succinic acid plant in Cassano Spinola, Italy. It has a capacity to produce around 10,000 tonnes of Biosuccinium succinic acid every year [4]. Myriant, as successor to BioEnergy International, have been awarded $50 million by the US Department of Energy to help fund the construction of a succinic acid plant in Louisiana, US. Scheduled for start-up in 2013, the plant will produce about 14.000 tonnes of bio-succinic acid annually. The technology is based on Myriant’s proprietary fermentation complemented by ThyssenKrupp Uhde’s downstream process. [5]. BASF and Purac (a subsidiary of CSM) are establishing a joint venture for the production and sale of biobased succinic

acid. The to be formed company with the name Succinity GmbH intends to be operational in 2013. A modified existing fermentation facility in Spain was announced to commence operations in late 2013 with an annual capacity of 10,000 tonnes of succinic acid [8]. Mitsubishi Chemicals and PTT are jointly investigating the feasibility of the manufacture of bio-based polybutylene succinate (PBS) in Thailand. BioAmber will be the supplier of biobased succinic acid to a Faurecia-Mitsubishi Chemical partnership for the production of PBS for automotive interior applications [9]. A similar approach is perfomed by Showa Denko K.K (SDK), who announced Myriant as its global supplier of biosuccinic acid for the production of PBS [5].

Feedstock First generation of succinic acid fermentation processes use traditional feedstock like starch hydrolysate, molasses or industrial sugars. In the near future this will shift to lignocellulose based fermentation feedstocks, as they are being developed for second generation bio-ethanol [10].

Applications Bio-based succinic acid can for example replace fossilbased succinic acid or adipic acid used for the manufacture of polyester polyols and polyurethanes. Another field of application is the manufacture of polybutylene succinate (PBS) (Fig. 3), a biodegradable polymer sold under brand names such as Bionolle® and GS

bioplastics MAGAZINE [03/13] Vol. 8

/PU BMM DIFNJDBMT BSF DSFBUFE FRVBM5. PlaÂŽ. These resins can for example be used as mulch films, rubbish bags and â&#x20AC;&#x2DC;flushableâ&#x20AC;&#x2122; hygiene products [4]. Polyamides are made by polycondensation of dicarbonic acids with diamines or by polyaddition of lactames. e.g. PA 66 or PA 6. Succinic acid and its derivates 1,4 â&#x20AC;&#x201C;di-amino butane or 2-pyrrolidinone are therefore raw materials for the production of polyamide 4.4 or polyamide 4 [3]. Other applications include thermoset resins, pigments, phthalate free plasticizers, coating components, adhesives, sealants, personal care ingredients and more. As an acidulant and preservative made from plant based feedstocks, bio-succinic acid offers multi-functionality with a unique flavor profile to food and flavor formulations [1]. Bio-based succinic acid can also serve as a building block for large volume chemical intermediates such as 1,4-butanediol (bio-BDO) [11].

Environmental Sustainability Benefits Todayâ&#x20AC;&#x2122;s technology for the production of succinic acid from biomass can realise up to 99.4% reduction in greenhouse gas (GHG) emissions compared to the production of equivalent petrochemical products [11]. With R&D development, succinic acid production from maize could lead to non-renewable energy savings of 51 to 68 GJ/tonne (53-71%) compared to petrochemical production via maleic acid. Lignocellulosic feedstock could increase this saving to 61-82%. The land requirement for shifting to future biotechnology production ranges from 0.07 to 0.32 ha/tonne depending on technology and feedstock [12].

.ZSJBOU JT UVSOJOH UIF QFUSPDIFNJDBM JOEVTUSZ HSFFO 8JUI PVS Ç˘BHTIJQ CJP TVDDJOJD BDJE GBDJMJUZ TMBUFE UP CFHJO DPNNFSDJBM QSPEVDUJPO JO FBSMZ .ZSJBOU JT QSPWJOH UIBU oOPU BMM DIFNJDBMT BSF DSFBUFE FRVBMp Ĺ JT NJMMJPO QPVOE DBQBDJUZ QMBOU XJMM CF UIF Ç STU PG JUT LJOE BOE TDBMF JO UIF 6OJUFE 4UBUFT UP QSPEVDF TVDDJOJD BDJE GSPN SFOFXBCMF GFFETUPDLT .ZSJBOUnT CJP TVDDJOJD CJP TVDDJOJD BDJE XJMM FOBCMF PVS DVTUPNFST UP JNQSPWF UIF TVTUBJOBCJMJUZ PG UIFJS QSPEVDUT XIJMF NBJOUBJOJOH QFSGPSNBODF BOE XJUIPVU QBZJOH B HSFFO QSJDF QSFNJVN 5P PSEFS B TBNQMF FNBJM VT BU QSPEVDUJOGP!NZSJBOU DPN

[1] http://www.bio-amber.com/products/en/products/succinic_ acid [2] N.N.: Wikipedia [3] N.N.: Polyamide from bio-amber, bioplastics MAGAZINE 01/2006 [4] N.N.: NNFCC Renewable Chemicals Factsheet: Succinic Acid, 2013 [5] http://www.myriant.com [6] BioAmber â&#x20AC;&#x201C; personal information, 30 April 2013 [7] Smidt, M.: A sustainable supply of succinic acid; Euro|Biotech|News No. 11-12, Vol. 10, 2011 [8] N.N.: BASF and CSM establish 50-50 joint venture for biobased succinic acid, Press-Release P-12-444, basf.com, 2012 [9] N.N.: Biobased succinic acid for PBS â&#x20AC;&#x201C; production capacities to be confirmed in 2013, European Bioplastics Bulletin 01/2013 [10] N.N.: personal information, Reverdia, May 2013 [11] N.N.: BioAmber Bio-SAâ&#x201E;˘ Earns High Score in Environmental Leader Technology Reviews; BioAmber Press Release, March 4, 2013 [12] The BREW Project. Medium and Long-term Opportunities and Risks of the Biotechnological Production of Bulk Chemicals from Renewable Resources â&#x20AC;&#x201C; The Potential of White Biotechnology; 2006. www.reverdia.com www.bio-amber.com www.myriant.com www.basf.com www.m-kagaku.co.jp/english/newsreleases www.purac.com

bioplastics MAGAZINE [03/13] Vol. 8

Opinion

Market studies by Michael Carus, nova-Institute

he nova-Institute carried out the study ‘Biobased Polymers in the World; Capacities, Production and Applications: Status Quo and Trends towards 2020’ in collaboration with renowned international experts from the field of biobased polymers. Considerably higher production capacity was found than in previous studies. The 4.6 million tonnes represent a share of 2% of an overall structural polymer production of 235 million tonnes in 2012. The table below shows for example the data of the latest market study from ifBB in comparison with nova’s findings for the year 2012. What are the reasons for this huge difference? 1) It is the first time that a study has looked at every kind of biobased polymer and their precursors, now including 48 polymers and 65 building blocks produced by 247 companies at 363 locations around the world and it examines in detail 12 biopolymer families produced by 114 companies in 135 locations (see table). 2) Following the focus on polymers in structural applications, Cellulose Acetate was included from the group of cellulosebased polymers. Other Cellulose derivatives are either used in functional applications or closely related to paper due to their production process (which is out of scope).

3) The capacities for PET are derived from the capacities of its precursor bio-MEG (Monoethylene glycol) which represents the bottleneck in the production of bio-PET right now. 4) The study also covers the large group of thermosets like epoxy resins, alkyd resins, unsaturated polyester resins and several others, based on natural oil polyols. Due to the structure of the value chain, the capacities here are derived from capacities and development of their precursors. Polyurethanes are regarded separately, as an own group of polymers, be they thermosetting or thermoplastic. 5) For PA, PUR and starch blends higher capacities were found, that information mainly comes directly from the processing companies.

Methodology of the nova study This study focuses exclusively on bio-based polymer producers, and the market data therefore does not cover the bio-based plastics branch in an attempt to avoid double counting over the various steps in the value chain. For more details about the methodology see issue 02/2013 of bioplastics MAGAZINE or http://bit.ly/X4ILj9 www.nova-institute.com

ifBB 2013 (European Bioplastics)

nova-Institut Bio-based polymers Cellulose Acetate

Producing companies until 2020 9

Locations 15

Production capacities in 2012 (t/a) 835.000

Production capacities in 2012 (t/a) 34.000

Cellulose Derivatives / Regenerated Cellulose

70.000

23.000

PBS / PBAT

175.000

122.000

250

PCL

1.250 200.000

200.000

PET

850.000

542.000

PHAs

30.000

21.750

PLA

190.000

186.000

PUR

150.000

1.250

PVC

Starch Blends

335.000

140.000

n.a.**

1.775.000

2.500

114

135

4.610.000

1.274.000

133

228

247

363

Thermosets TPE Total Additional companies included in the “Bio-based Polymer Producer Database” Total companies and locations recorded in the Market Study

Including Joint Venture of two companies sharing one location, counting as two The final composition of a thermoset is not determined by the big chemical companies, but by multitude of formulators. In order to get capacitites’ data it is necessary to look at the renewable building blocks (monomeric and polymeric) that are used for thermosets. *

bioplastics MAGAZINE [03/13] Vol. 8

Opinion

Reliable and transparent by Constance Ißbrücker, European Bioplastics

ompared to conventional plastics, the bioplastics market is a fairly young one. Currently, there is no common systematization for bioplastics statistics available. The consequence: Diverse reports from private and public organisations and institutions try to give an impression of where the market stands and where it is heading. Different methodological approaches with varying levels of thoroughness are published. Reports giving not one common, but quite a multitude of impressions are the consequence. This is confusing for the end consumer, and also on a B2B level. What is really included in the data? Which forecasts are reliable? These were leading questions, when European Bioplastics stepped up its own statistical approach together with an independent research facility, the Institute for Biocomposites and Bioplastics (IfBB, University of Applied Arts Hanover/Germany). The aim was, to provide reliable, transparent market data giving a neutral overview close to the reality of the bioplastics market. The survey of EuBP and the IfBB comprises data regarding production capacities (actual and announced) of bioplastic worldwide. 115 manufacturers, which play a significant role on the market concerning production capacities, were identified. The current statistics comprise the data of 70 manufacturers from 19 countries and 87 material types. Still, all relevant market players are accounted for, and the survey gives an indicative overview of the market situation. In order to account for the volatility of the market, a conservative approach was taken for the accumulation and assessment of the data. EuBP defines bioplastics as biobased, biodegradable or both. The published statistics consider novel and upcoming bioplastics, which is the market the association is representing and whose growth is explained. Traditional materials such as rubber, but also established cellulose derivatives and regenerates in their long familiar applications are not included. To ensure a welldefined scope of the data, precursors and intermediates (like for thermosets) were not included. This results in a strong focus on thermoplastic materials. Functional biomass polymers like WPC were excluded for the same reason as starch-filled polyolefines. In contrast, blends based on plastified starch, in which the polysaccharide does not only act as filling material, were considered. The relatively short reference period from 2011 to 2016 was chosen, as market activities are subject to variations, and a broader timeframe would decrease the validity of the resulting data. At the end of 2012, no announcements for production capacities that went beyond 2016 were known of. If production capacities are announced for a later date (e.g. middle of the year), capacities are partially calculated based on the facility’s total capacity. The total amount is then counted for in the year to follow.

bioplastics MAGAZINE [03/13] Vol. 8

The method of counting production capacities per manufacturer inevitably leads to double counting. Therefore, functional components are subtracted from blends to obtain a realistic assessment of the total market volume. This concerns e.g. for PLA or starch, blended with e.g. PBAT. To give a correct projection of the realistic production development of a facility, the following assumptions were made: For all those interested in European Bioplastics’ methodology the following link provides more information: http://en.european-bioplastics.org/market/marketdevelopment/market-data-methodology

Production capacity development

Production capacity Linear regression Logistic regression

2010 20111 20122 2013 2014 20153 20164 2017 Announcement of production start (logistic1 / linear2) Expected point of full capacity (linear3 / logistic4) Capacity growth of < 10,000 t/a: Forward projection of announced capacities Capacity growth 10,000 – 50,000 t/a: Equalisation and growth function (linear regression): f(x)=m∙x+b Capacity growth of > 50,000 t/a: Equalisation and growth function (logistic regression):

Scope of considered materials in the bioplastics statistics (EuBP/IfBB) Biodegradable Material group Abbreviation Cellulose derivatives1 Regenerated cellulose2 Other biodegradable polyesters PBAT, PBS, PCL Polyhydroxyalkanoates PHA Polylactic acid incl. blends PLA, PLA-Blends Starch blends (biodegradable) Biobased, durable Material group Abbreviation Polyamide Bio-PA Bio-PP Polypropylene3 Polyethylene Bio-PE Polyurethane Bio-PUR Bio-PET Polyethylene terephthalate4 Thermoplastic elastomers Bio-TPE Bio-PC Polycarbonates6 PEF Polyethylenefuranoate7 1 Cellulose ester only 2 Hydrated cellulose foils certified to be compostable (in packaging segment). 3 At the time of publication, bio-PP was in its development stage. 4 Bio-PET 30: Considered to be 30 % biobased, bio-PET 100: Considered to be 100 % biobased. 5 Excluding starch filled polyolefins. 6 At the time of publication, bio-polycarbonate was in its development stage. 7 At the time of publication, bio-PEF was in its development stage.

bioplastics MAGAZINE [03/13] Vol. 8

Suppliers Guide 1. Raw Materials 10

Showa Denko Europe GmbH Konrad-Zuse-Platz 4 81829 Munich, Germany Tel.: +49 89 93996226 www.showa-denko.com support@sde.de

www.cereplast.com US: Tel: +1 310.615.1900 Fax +1 310.615.9800 Sales@cereplast.com Europe: Tel: +33 680 28 69 99 fdevivie@cereplast.com

Natur-Tec® - Northern Technologies 4201 Woodland Road Circle Pines, MN 55014 USA Tel. +1 763.225.6600 Fax +1 763.225.6645 info@natur-tec.com www.natur-tec.com

Simply contact:

Tel.: +49 2161 6884467

suppguide@bioplasticsmagazine.com 70

Stay permanently listed in the Suppliers Guide with your company logo and contact information.

For only 6,– EUR per mm, per issue you can be present among top suppliers in the field of bioplastics.

For Example:

DuPont de Nemours International S.A. 2 chemin du Pavillon 1218 - Le Grand Saconnex Switzerland Tel.: +41 22 171 51 11 Fax: +41 22 580 22 45 plastics@dupont.com www.renewable.dupont.com www.plastics.dupont.com

Kingfa Sci. & Tech. Co., Ltd. No.33 Kefeng Rd, Sc. City, Guangzhou Hi-Tech Ind. Development Zone, Guangdong, P.R. China. 510663 Tel: +86 (0)20 6622 1696 info@ecopond.com.cn www.ecopond.com.cn FLEX-162 Biodeg. Blown Film Resin! Bio-873 4-Star Inj. Bio-Based Resin!

PolyOne Avenue Melville Wilson, 2 Zoning de la Fagne 5330 Assesse Belgium Tel.: + 32 83 660 211 www.polyone.com

100

120

130

39 mm

110

Polymedia Publisher GmbH Dammer Str. 112 41066 Mönchengladbach Germany Tel. +49 2161 664864 Fax +49 2161 631045 info@bioplasticsmagazine.com www.bioplasticsmagazine.com

140

Sample Charge: 150

160

39mm x 6,00 € = 234,00 € per entry/per issue

Sample Charge for one year: 6 issues x 234,00 EUR = 1,404.00 €

170

180

The entry in our Suppliers Guide is bookable for one year (6 issues) and extends automatically if it’s not canceled three month before expiry.

Jincheng, Lin‘an, Hangzhou, Zhejiang 311300, P.R. China China contact: Grace Jin mobile: 0086 135 7578 9843 Grace@xinfupharm.com Europe contact(Belgium): Susan Zhang mobile: 0032 478 991619 zxh0612@hotmail.com www.xinfupharm.com 1.1 bio based monomers

PURAC division Arkelsedijk 46, P.O. Box 21 4200 AA Gorinchem The Netherlands Tel.: +31 (0)183 695 695 Fax: +31 (0)183 695 604 www.purac.com PLA@purac.com

190

200

210

1.2 compounds

220

230

240

250

www.facebook.com www.issuu.com

260

www.twitter.com 270

www.youtube.com

bioplastics MAGAZINE [03/13] Vol. 8

API S.p.A. Via Dante Alighieri, 27 36065 Mussolente (VI), Italy Telephone +39 0424 579711 www.apiplastic.com www.apinatbio.com

FKuR Kunststoff GmbH Siemensring 79 D - 47 877 Willich Tel. +49 2154 9251-0 Tel.: +49 2154 9251-51 sales@fkur.com www.fkur.com

GRAFE-Group Waldecker Straße 21, 99444 Blankenhain, Germany Tel. +49 36459 45 0 www.grafe.com

Guangdong Shangjiu Biodegradable Plastics Co., Ltd. Shangjiu Environmental Protection Eco-Tech Industrial Park,Niushan, Dongcheng District, Dongguan City, Guangdong Province, 523128 China Tel.: 0086-769-22114999 Fax: 0086-769-22103988 www.999sw.com www.999sw.net 999sw@163.com

WinGram Industry CO., LTD Great River(Qin Xin) Plastic Manufacturer CO., LTD Mobile (China): +86-13113833156 Mobile (Hong Kong): +852-63078857 Fax: +852-3184 8934 Email: Benson@wingram.hk 1.3 PLA

Shenzhen Esun Ind. Co;Ltd www.brightcn.net www.esun.en.alibaba.com bright@brightcn.net Tel: +86-755-2603 1978 1.4 starch-based bioplastics

Limagrain Céréales Ingrédients ZAC „Les Portes de Riom“ - BP 173 63204 Riom Cedex - France Tel. +33 (0)4 73 67 17 00 Fax +33 (0)4 73 67 17 10 www.biolice.com

BIOTEC Biologische Naturverpackungen Werner-Heisenberg-Strasse 32 46446 Emmerich/Germany Tel.: +49 - 2822 - 925110 info@biotec.de www.biotec.de

Suppliers Guide 1.6 masterbatches

3. Semi finished products 3.1 films

ROQUETTE 62 136 LESTREM, FRANCE 00 33 (0) 3 21 63 36 00 www.gaialene.com www.roquette.com

Grabio Greentech Corporation Tel: +886-3-598-6496 No. 91, Guangfu N. Rd., Hsinchu Industrial Park,Hukou Township, Hsinchu County 30351, Taiwan sales@grabio.com.tw www.grabio.com.tw

GRAFE-Group Waldecker Straße 21, 99444 Blankenhain, Germany Tel. +49 36459 45 0 www.grafe.com

PolyOne Avenue Melville Wilson, 2 Zoning de la Fagne 5330 Assesse Belgium Tel.: + 32 83 660 211 www.polyone.com

Huhtamaki Films Sonja Haug Zweibrückenstraße 15-25 91301 Forchheim Tel. +49-9191 81203 Fax +49-9191 811203 www.huhtamaki-films.com

www.earthfirstpla.com www.sidaplax.com www.plasticsuppliers.com Sidaplax UK : +44 (1) 604 76 66 99 Sidaplax Belgium: +32 9 210 80 10 Plastic Suppliers: +1 866 378 4178

2. Additives/Secondary raw materials

PSM Bioplastic NA Chicago, USA www.psmna.com +1-630-393-0012 1.5 PHA

Arkema Inc. Functional Additives-Biostrength 900 First Avenue King of Prussia, PA/USA 19406 Contact: Connie Lo, Commercial Development Mgr. Tel: 610.878.6931 connie.lo@arkema.com www.impactmodifiers.com

A & O FilmPAC Ltd 9 Osier Way Olney, Bucks. MK46 5FP Tel.: +44 1234 714 477 Fax: +44 1234 713 221 sales@bioresins.eu www.bioresins.eu

TianAn Biopolymer No. 68 Dagang 6th Rd, Beilun, Ningbo, China, 315800 Tel. +86-57 48 68 62 50 2 Fax +86-57 48 68 77 98 0 enquiry@tianan-enmat.com www.tianan-enmat.com

NOVAMONT S.p.A. Via Fauser , 8 28100 Novara - ITALIA Fax +39.0321.699.601 Tel. +39.0321.699.611 www.novamont.com

President Packaging Ind., Corp. PLA Paper Hot Cup manufacture In Taiwan, www.ppi.com.tw Tel.: +886-6-570-4066 ext.5531 Fax: +886-6-570-4077 sales@ppi.com.tw

4. Bioplastics products

GRAFE-Group Waldecker Straße 21, 99444 Blankenhain, Germany Tel. +49 36459 45 0 www.grafe.com Metabolix 650 Suffolk Street, Suite 100 Lowell, MA 01854 USA Tel. +1-97 85 13 18 00 Fax +1-97 85 13 18 86 www.mirelplastics.com

Taghleef Industries SpA, Italy Via E. Fermi, 46 33058 San Giorgio di Nogaro (UD) Contact Frank Ernst Tel. +49 2402 7096989 Mobile +49 160 4756573 frank.ernst@ti-films.com www.ti-films.com

Minima Technology Co., Ltd. Esmy Huang, Marketing Manager No.33. Yichang E. Rd., Taipin City, Taichung County 411, Taiwan (R.O.C.) Tel. +886(4)2277 6888 Fax +883(4)2277 6989 Mobil +886(0)982-829988 esmy@minima-tech.com Skype esmy325 www.minima-tech.com

The HallStar Company 120 S. Riverside Plaza, Ste. 1620 Chicago, IL 60606, USA +1 312 385 4494 dmarshall@hallstar.com www.hallstar.com/hallgreen

Cortec® Corporation 4119 White Bear Parkway St. Paul, MN 55110 Tel. +1 800.426.7832 Fax 651-429-1122 info@cortecvci.com www.cortecvci.com

WEI MON INDUSTRY CO., LTD. 2F, No.57, Singjhong Rd., Neihu District, Taipei City 114, Taiwan, R.O.C. Tel. + 886 - 2 - 27953131 Fax + 886 - 2 - 27919966 sales@weimon.com.tw www.plandpaper.com

Eco Cortec® 31 300 Beli Manastir Bele Bartoka 29 Croatia, MB: 1891782 Tel. +385 31 705 011 Fax +385 31 705 012 info@ecocortec.hr www.ecocortec.hr

Rhein Chemie Rheinau GmbH Duesseldorfer Strasse 23-27 68219 Mannheim, Germany Phone: +49 (0)621-8907-233 Fax: +49 (0)621-8907-8233 bioadimide.eu@rheinchemie.com www.bioadimide.com

bioplastics MAGAZINE [03/13] Vol. 8

Suppliers Guide 6. Equipment

6.1 Machinery & Molds

Simply contact:

Tel.: +49 2161 6884467

suppguide@bioplasticsmagazine.com 70

Stay permanently listed in the Suppliers Guide with your company logo and contact information.

For only 6,– EUR per mm, per issue you can be present among top suppliers in the field of bioplastics.

For Example: 100

130

39 mm

110

120

Polymedia Publisher GmbH Dammer Str. 112 41066 Mönchengladbach Germany Tel. +49 2161 664864 Fax +49 2161 631045 info@bioplasticsmagazine.com www.bioplasticsmagazine.com

140

Sample Charge: 150

160

Molds, Change Parts and Turnkey Solutions for the PET/Bioplastic Container Industry 284 Pinebush Road Cambridge Ontario Canada N1T 1Z6 Tel. +1 519 624 9720 Fax +1 519 624 9721 info@hallink.com www.hallink.com

39mm x 6,00 € = 234,00 € per entry/per issue

Sample Charge for one year:

Uhde Inventa-Fischer GmbH Holzhauser Strasse 157–159 D-13509 Berlin Tel. +49 30 43 567 5 Fax +49 30 43 567 699 sales.de@uhde-inventa-fischer.com Uhde Inventa-Fischer AG Via Innovativa 31 CH-7013 Domat/Ems Tel. +41 81 632 63 11 Fax +41 81 632 74 03 sales.ch@uhde-inventa-fischer.com www.uhde-inventa-fischer.com

180

Roll-o-Matic A/S Petersmindevej 23 5000 Odense C, Denmark Tel. + 45 66 11 16 18 Fax + 45 66 14 32 78 rom@roll-o-matic.com www.roll-o-matic.com

ProTec Polymer Processing GmbH Stubenwald-Allee 9 64625 Bensheim, Deutschland Tel. +49 6251 77061 0 Fax +49 6251 77061 500 info@sp-protec.com www.sp-protec.com

Saida FDS Incorporated 3-6-6 Sakae-cho, Yaizu, Shizuoka, Japan Tel : +81-90-6803-4041 info@saidagroup.jp www.saidagroup.jp

200

10.1 Associations

9. Services

Osterfelder Str. 3 46047 Oberhausen Tel.: +49 (0)208 8598 1227 Fax: +49 (0)208 8598 1424 thomas.wodke@umsicht.fhg.de www.umsicht.fraunhofer.de

Institut für Kunststofftechnik Universität Stuttgart Böblinger Straße 70 70199 Stuttgart Tel +49 711/685-62814 Linda.Goebel@ikt.uni-stuttgart.de www.ikt.uni-stuttgart.de

BPI - The Biodegradable Products Institute 331 West 57th Street, Suite 415 New York, NY 10019, USA Tel. +1-888-274-5646 info@bpiworld.org

European Bioplastics e.V. Marienstr. 19/20 10117 Berlin, Germany Tel. +49 30 284 82 350 Fax +49 30 284 84 359 info@european-bioplastics.org www.european-bioplastics.org

10.2 Universities

6.2 Laboratory Equipment

The entry in our Suppliers Guide is bookable for one year (6 issues) and extends automatically if it’s not canceled three month before expiry. MODA : Biodegradability Analyzer

190

10. Institutions

8. Ancillary equipment

6 issues x 234,00 EUR = 1,404.00 € 170

UL International TTC GmbH Rheinuferstrasse 7-9, Geb. R33 47829 Krefeld-Uerdingen, Germany Tel: +49 (0)2151 88 3324 Fax: +49 (0)2151 88 5210 ttc@ul.com www.ulttc.com

narocon Dr. Harald Kaeb Tel.: +49 30-28096930 kaeb@narocon.de www.narocon.de

IfBB – Institute for Bioplastics and Biocomposites University of Applied Sciences and Arts Hanover Faculty II – Mechanical and Bioprocess Engineering Heisterbergallee 12 30453 Hannover, Germany Tel.: +49 5 11 / 92 96 - 22 69 Fax: +49 5 11 / 92 96 - 99 - 22 69 lisa.mundzeck@fh-hannover.de http://www.ifbb-hannover.de/

7. Plant engineering 210

220

EREMA Engineering Recycling Maschinen und Anlagen GmbH Unterfeldstrasse 3 4052 Ansfelden, AUSTRIA Phone: +43 (0) 732 / 3190-0 Fax: +43 (0) 732 / 3190-23 erema@erema.at www.erema.at

230

240

250

www.facebook.com www.issuu.com

260

www.twitter.com 270

www.youtube.com

bioplastics MAGAZINE [03/13] Vol. 8

nova-Institut GmbH Chemiepark Knapsack Industriestrasse 300 50354 Huerth, Germany Tel.: +49(0)2233-48-14 40 E-Mail: contact@nova-institut.de

Bioplastics Consulting Tel. +49 2161 664864 info@polymediaconsult.com

Michigan State University Department of Chemical Engineering & Materials Science Professor Ramani Narayan East Lansing MI 48824, USA Tel. +1 517 719 7163 narayan@msu.edu

Events

Event Calendar

Subscribe now at bioplasticsmagazine.com the next six issues for €149.–1)

Biopolymere in der Spritzgussverarbeitung 06.06.2013 - Hannover, Germany

Special offer for students and young professionals1,2) € 99.-

http://wip-kunststoffe.de/wip/top/967572-biopolymere-schon-verarbeitet/

Biopolymers Symposium 2013

11.06.2013 - 12.06.2013 - Chicago,IL,USA http://www.biopolymersummit.com/biopolymers-agenda.aspx

Biochemicals & Bioplastics 2013 Summit

2) aged 35 and below. Send a scan of your student card, your ID or similar proof ...

19.06.2013 - 20.06.2013 - Frankfurt, Germany http://www.acius.net

BioPlastek 2013 Forum

26.06.2013 - 28.06.2013 - San Francisco (CA), USA San Francisco Hilton (Financial District) www.bioplastek.com

The 5th International Conference on Sustainable Materials, Polymers and Composites 03.07.2013 - 04.07.2013 - Birmingham, (UK) Großbritannien http://www.ecocomp-conference.com

4th International Conference on BIOFOAMS 2013 27.08.2013 - 01.01.1970 - Toronto- Canada http://biofoams2013.mie.utoronto.ca/

2nd Conference on CO2 as Feedstock for Chemistry and Polymers 07.10.2013 - 09.10.2013 - Essen, Germany Haus der Technik http://www.co2-chemistry.eu

Fifth German WPC Conference

10.12.2013 - 11.12.2013 - Cologne, Germany Maritim Hotel Cologne http://www.wpc-kongress.de/registration?lng=en

8th European Bioplastics Conference

10.12.2013 - 11.12.2013 - Berlin, Germany InterContinental Hotel www.conference.european-bioplastics.org

Innovation Takes Root

17.02.2014 - 19.02.2014 - Orlando FL, USA Orlando World Center Marriott http://www.innovationtakesroot.com/

World Bio Markets 2014

04.03.2014 - 06.03.2014 - Amsterdam, The Netherlands RAI Amsterdam http://www.worldbiofuelsmarkets.com

BioPlastics 2014: The Re-Invention of Plastics 04.03.2014 - 06.03.2014 - Las Vegas, NV, USA Caesars Palace http://www.BioplastConference.com

Mention the promotion code ‘watch‘ or ‘book‘ and you will get our watch or the book3) Bioplastics Basics. Applications. Markets. for free 1) Offer valid until 31 Dec. 2013 3) Gratis-Buch in Deutschland nicht möglich, no free book in Germany

bioplastics MAGAZINE [03/13] Vol. 8

Companies in this issue Company

Editorial Advert

4e solutions

A&O FilmPAC

66, 67

President Packaging

ProTec Polymer Processing

PSM

Gruppo M&G

Amyris

Guangdong Shangjiu 66

Arkema

Guangzhou Bioplus

9, 16, 61

Hallstar

PTT

Reverdia

Rewe

Purac

Hirsch

Rhein Chemie

Bayer Material Science

HS Merseburg

Roll-o-Matic

Belgian Packaging Inst.

Hubei Guanghe

Roquette

Bio Energy Intl.

Huhtamaki

BioAmber

IHS Chemical

BIOCOPACK

Institut for bioplastics & biocomposites (IfBB)

BioFactur

Institut für Kunststofftechnik

Biome Bioplastics

Biotec

BKR Kreyenborg

BPI

66 31

Hallink 67

BASF

Editorial Advert

Company

GroenBeker

Adsale (Chinaplas)

ARD

Editorial Advert

Grafe 67

API

67 68 34, 61

Rotec

RWTH Aachen University

Saida

Sarad

Institut für Kunststoffverarbeitung (IKV)

Shandong Fuwin

Interfacial Solutions

Shanghai Disoxidation

ITENE

Shenzhen Esun

IWT

Showa Denko

Jiangsu Jinhe

Sidaplax

Bremen Univ. App. Sc.

Johann Borgers

SSICA

Brno Univ. of. Techn.

Kingfa

Starlinger

Cardia Bioplastics

Kuraray

Succinity

Cargill

Limagrain Céréales Ingrédients

Sulzer

Celabor

Loopline Polymers

Taghleef Industries

Ludwig Maximilians Univ. München

Technalia

66 6 66

67 12

Clariant

Memo

CO2 Starch

Messe Düsseldorf (K'2013)

Teijin

Metabolix

ThyssenKrupp Uhde

Coperion

9, 33

Cortec

CPD CreaCycle CSM

MF Folien

Michigan State University

Minima Technology

7, 61

Mitsubishi Chemical

Tecnaro

2, 22

TianAn Biopolymer

Tianjin Greenbio

Toray

Toyota

Devetex

Myriant

Doraplast

Nafigate

UL Thermoplastics

NaKu

Univ. App. Sc. Fulda

Univ. Ghent

Univ. Nottingham

Univ. Sheffield

DSM

35, 61

DuPont

9, 32

EREMA

17, 68

NatureWorks

11, 64

19, 68

Natur-Tec

European Bioplastics

narocon

68 9, 48, 53 66

Uhde Inventa-Fischer

68 68

FAO

New Sunrise Plastics

Univ. Sydney

fischerwerke

Newlight Technologies

9, 14

Univ. Toronto

FKuR

Flanders Plastic Vision

NNFCC

Flexform

nova-Institut

Fraunhofer IVV

Novamont

Fraunhofer LBF

Ökologische Molkereien Allgäu Plantic

Fraunhofer UMSICHT

2, 66

Fukutomi

Futerro

Gala Galactic

Editorial Planner

Univ. Warwick

Univ. Wisconsin

13, 68

USDA

67, 72

UW Steven Point

Waschbär

Wei Mon

60 9, 10, 63

plasticker

3, 48

Grabio Greentech

NGR

Plastic Suppliers 41

PoliKompleks

Well Water

WinGram

polymediaconsult 67

66, 67

Zéfal

Publ.-Date

edit/ad/ Deadline

04/2013

Jul/Aug

05.08.13

05/2013

Sept/Oct

06/2013

Nov/Dec

66 33 34

Zhejiang Hangzhou Xinfu

2013

Month

65, 67 21

Wuhan Huali 688

PolyOne

Issue

Subject to changes

Editorial Focus (1)

Editorial Focus (2)

Basics

05.07.13

Bottles / Blow Moulding

Bioplastics in Building & Construction

Land use for bioplastics (update)

01.10.13

01.09.13

Fiber / Textile / Nonwoven

Designer‘s Requirements for Bioplastics

biobased (12C / 14C vs. Biomass)

K'2013 Preview

02.12.13

02.11.13

Films / Flexibles / Bags

Consumer Electronics

Eutrophication (t.b.c)

K'2013 Review

bioplastics MAGAZINE [03/13] Vol. 8

3, 7, 35, 54, 61

Braskem

Cereplast

Company

Fair Specials

2013

P R E S E N T S

THE EIGHTH ANNUAL GLOBAL AWARD FOR DEVELOPERS, MANUFACTURERS AND USERS OF BIO-BASED PLASTICS.

Call for proposals

til Please let us know un

August 31st:

and does rvice or development is se t, uc od pr e th at Wh 1. n an award development should wi or ce rvi se t, uc od pr is 2. Why you think th ganisation does oposed) company or or pr e th (or ur yo at Wh 3. ay also (approx 1 page) and m s rd wo 0 50 ed ce ex t d/or Your entry should no marketing brochures an t be s, ple m sa , hs ap gr oto The 5 nominees mus be supported with ph (cannot be sent back). ion tat en m cu do l ica techn 30 second videoclip prepared to provide a ded from

try form can be downloa More details and an en ine.de/award www.bioplasticsmagaz

The Bioplastics Award will be presented during the 8th European Bioplastics Conference December 2013, Berlin, Germany

supported by

Sponsors welcome, please contact mt@bioplasticsmagazine.com

Enter your own product, service or development, or nominate your favourite example from another organisation

A real sign of sustainable development.

There is such a thing as genuinely sustainable development.

Since 1989, Novamont researchers have been working on an ambitious project that combines the chemical industry, agriculture and the environment: “Living Chemistry for Quality of Life”. Its objective has been to create products with a low environmental impact. The result of Novamont’s innovative research is the new bioplastic Mater-Bi®. Mater-Bi® is a family of materials, completely biodegradable and compostable which contain renewable raw materials such as starch and vegetable oil derivates. Mater-Bi® performs like traditional plastics but it saves energy, contributes to reducing the greenhouse effect and at the end of its life cycle, it closes the loop by changing into fertile humus. Everyone’s dream has become a reality.

Living Chemistry for Quality of Life. www.novamont.com

Inventor of the year 2007

Within Mater-Bi® product range the following certifications are available

The “OK Compost” certificate guarantees conformity with the NF EN 13432 standard (biodegradable and compostable packaging) 3_2012