BIOPOLYMERSBIOPOLYMERS

Market and technological new Market and technological new trendstrends

113 Enterprises

8 Industrial associations3 Foundations and public bodies

14 Universities1. Politecnico di Torino

2. Università Piemonte Orientale

3. Università di Genova

4. Università di Pisa

5. Università di Palermo

6. Università di Salerno

7. Università di Modena e Reggio Emilia

8. Università di Napoli

9. Università di Torino

10. Università di Messina

11. ICIMSI Supsi (Svizzera)

12. Università di Milano

13. Università di Camerino

14. Università degli studi di Brescia

Members

138 members

• Nanocomposite materials (POSS, nanoclay, nanotubes, etc.)• Recycling• Improvement of properties (fire retardancy, mechanical,

barrier, physical, weathering, thermal degradation, etc.)• Biopolymers (compounding and processing)

Research on Materials

Innovation in plastics area

• The continous contacts with the Companies of all the different sectors of plastics industry allow Proplast to sense the pulse of the plastics market even as regards research and innovations

Innovation in plastics area

Concerning innovation in plastics area, companies are today mainly interested in:

1. Optimization of parts manufacturing;2. New materials research

• Biopolymers• Nanocomposite

Innovation in plastics area

These companies interests are fully in line with plastics development trends

• In the ’80s, after the engineering plastics great success, HPP and advanced composites appeared as a great opportunity and many big companies invested in their research and production.

• In the ’90s, the economical crisis forced many companies to review their plans for the high costs involved and the low return on investment.

•Today HPP represent about 0.1-0.014% of the total plastics consumption.

Innovation in plastics areaAs a result, interest shifted towards the optimization of “traditional” polymer properties

• By compounding, additivation, copolymerization, etc..

• On the basis of end users requirements as well as processing technologies

Strategy for new polimeric materials intoduction:

Sell performances, not products!

Answer to Companies needs

Solve problems

Biopolymers

Biopolymers present great development possibilities, because they combine high

• technical potentialities and• ecosustainability,

either from the point of view of raw materials or from their end life recovery.

Biopolymers - Definition

Definition of “European Bioplastics Association”

�Compostable/Biodegradable polymers with approved biodegradability

� From renewable or fossil raw materials

�Polymers based on renewable raw materials� Biodegradable or not biodegradable

Today many different classes of materials fit into these classifications:

Biopolymers / Biobased Polymer

Renewable Resource-based

Petro-Bio (Mixed) Sources

Microbialsynthesized

Petro-based synthetic

• Polylactic acid, PLA

• Starch plastics

• Cellulosic plastic

• Soy-based plastic

• Polyhydroxyalkanoates, PHA

• Polyhydroxybutyrateco-valerate, PHBV

• Aliphatic polyesters

• Aliphatic-aromatic polyesters

• Polyester-amides

• Polyvinyl alcohols

• PTT

• BiobasedPolyurethane

• Biobasedepoxy

• Blends etc…

A bit of history

• Biopolymers have been on the market for a very long time. The first man-made polymers were based on renewable raw materials. With the development of the cheaper technologies based on fossil resources, their role became progressively less and less important.

• In the ’70s, started an intensive R&D activity to develop new classes of biopolymers, to be used mainly in packaging.

• The goal was to save fossil resources and to avoid environmental pollution.

Big chemical groups policy

• Many big chemical groups (ICI, Monsanto, P&G, Montedison, Dow, Bayer, Basf…) started to invest in biopolymers. Progressively, many of them stopped the activity or sold it to small companies specialized on biochemistry.

• In the last years, many of the same large groups are re-entering in the sector, especially with the new target of developing biomonomers (ethylene, acrylic, poyols) for the synthesis of “traditional” polymers.

Biopolymers Market• Today, biopolymers market is still a niche market, mainly restricted to packaging and agriculture areas. It could be evaluated around 0.3 – 0.4 % of the total plastics market (around 350.000 tons).

• Surveys of market request, conducted before 2006, forecasted the highest development in area of biodegradable polymers.

Biopolymers Market

In the last year, there was a considerable change on biopolymers development lines . It has been realized that, the traditional factors, which have, in the past, been the basis of R&D :

• More competitive price structure• Government / legislative laws• Degradability/compostability standard• Availability and optimization of composting

processesare no longer more sufficient.

Biopolymers Market

In order to allow biopolymers to have an important future from an industrial point of view, it is necessary to extend the use of biopolymers in the production of:

durable goods or structural applications(transportation, electro/electronics, appliances,

and so on).

Global Production Capacity of Bioplastics

(da fonte European Bioplastics 2007-2011)

Market development

This trend clearly emerged from the presentations and the subsequent discussions in the last European Bioplastics Association Conference. It is related to the following factors:

Market development

• Biopolymers development in the production of durable goods.

• The development of recycling techniques, in order to extend the useful life of biopolymers, compared to biodegradation/composting processes.

Obviously, biodegradation/compostability will remain fundamental factors for application tied to agriculture and packaging.

Industrial and structural application possibilities

Many companies, mainly Japanese, are operating along these lines:

• Toyota has the target to substitute with biopolymers 20% of polymers based on fossil resources, by the year 2020

• NEC target is the substitution of 10% within 2010

• Mazda has developed a dashboard prototype based on a PLA with improved impact and thermal resistance

Industrial and structural application possibilities

On the basis of the above points, very important research lines have been identified :

• Development of formulation which could allow the tailoring of biopolymers for specific applications , in line with the market trend in petrochemical polymers, which in turn requires a

� Development of additives and reinforcing agents by natural sources or biodegradable which can be incorporated into biopolymers.

•Development of biomonomers for the production of “traditional”polymers. In this case, additives could be not biodegradable.

Is this target achievable?

• Considering their properties, this target is achievable, as indicated by a recent report (2005) prepared by Utrecht University and Fraunhofer Institute for the European Commission’s IPTS. This study estimates that the technical substitution potential of biopolymers is 33% of the total polymer production (that is about 13.4 million tons in EU).

• According to the European Bioplastics Association the technical potential today could be estimated at 5-10% of the plastics consumption (in the long run: much higher).

Standard

This new approach requires that polymer manufacturers, compounders, converters, additives manufacturers and end users would have detailed information and knowledge on biodegradability and compostability behaviour and subsequent standard as a function of application.

Even if recycling is taken more in consideration, it could be interesting to evaluate the possibility at its end of life, to dispose of a part by biodegradation as alternative to energy recovery

Biodegradation Standard

in aqueous medium

CO2 convertionISO 14852

Biodegradation Standard

Aerobics test Anaerobics test

solidin aqueous medium

ISO 14853High solidISO 15985

O2consumptionISO 14851

CompostISO 14855

Mineral bed omposting

ISO 14855 emenda

In soil or landfill ISO 17556

CO2

production

Standard

In selecting additives in order to develop formulations that will allow tailoring biopolymers for specific application, it will benecessary to take in consideration that norms on biodegradation/compostability require that:

• toxic byproducts can not be released on the environment • heavy metal concentration must be below the level

allowed by legislation and, most importantly,• each component must be tested for

compostability/biodegradation

In detail:

Compostability evaluation – EN 13432

A plastic is compostable if:

• it is formed by components, which have been, each individually

qualified as compostable.

•The analysis of compostability of a packaging is simplified and traced

back to the analysis of compostability of the single constitutive material.

•Constituents below 1% must not be evaluated as long as the total of

these constituents is below 5%.

The same concept is reported on EN 14995, related to Plastics

materials.

Bioadditives

Many companies are working to develop and offering products on the market. Proplast has presented a regional project on this topics. One of the target is centered on the study of all the available additives for biopolymers.

Information on additives are available on the various sites of certification systems (ex. DIN Certco, Vinçotte, ecc…)

Bioadditive - examplesClariant is very active and it is offering a large portfolio of products, including masterbatches :

• additive to assist biodegradability (Cesa-oxo) • conventional pigments in biopolymers carriers (food

approved) and /or with “ecotox” certification meeting EN 13432 soil toxicity requirements (Renol masterbatches)

• natural pigments in a range of conventional and biopolymers carriers (Renol Natur)

• additive suitable in case of macromoleculare fracture (Cesa Extend)

Bioadditive - examples

PolyOne is also very active. Among its additives it is possible to quote :

• masterbatches of colors on biopolymers carrier (OnColor BIO Colorant)

• antislip and antiblocking agents for different biopolymers and

• specific additives mainly for PLA (antistatic, impact improvers, antiUV (OnCap Bio)

Bioadditive - example• Sukano , beside production of compounds, is offering masterbatches of

different colours, antistatic, anti UV, processing aids, impact improvers, mould release agent antislip, antiblocking, nucleating agents mainly for PLA

• Rohm&Haas presents additives on line with its experience: PLA

impact improvers (Paraloid), melt strength improvers, adhesive for film lamination

• DuPont presents a range of products to improve toughness and thermal resistance (Biomax)

• Arkema impact modifier (BioStrenght)

• Dainichiseika has developed a series of rotogravure print inks

• Polnox Corp. antioxidants for PLA

• In Italy Frilvam and Viba claims to be active in this sector

Bioadditive

Biofibers represent another very important class of additives

As in case of petrochemicals polymers, addition of reinforcing fibers increases thermal, mechanical, and structural properties.

Control of fiber orientation “optimizes” properties

Biocomposites vs Bioplastics?Today there are only few examples of applications in biocomposites based on biopolymers and natural fibers. Most known is the case of mobile phone made by NEC, in cooperation with Unitika, based on kenaf reinforced PLA. Several studies are under development with various universities and research institutions on other types of biopolymers and natural fibers

Natural fibers are more used with petrochemical polymers. In the automotive sector, natural fibers allow a consistent weight reduction (with consequent fuel reduction) and make easier the part recovery.

BiofibersIn comparison to inorganic fibers, vegetable fibers present :

Advantages• Renewability and high availability• Biodegradability• Lower recycling problems. In energy recovery plant they could be

burned• Low density with consequent high specific properties• Lower abrasion during processing• Thermal and acoustic insulation due to their cellular and hollow

structure• Lower cost

Biofibers

Disadvantages

• Variability of properties as a function of production sites and seasons

• Incompatibility with hydrophobic polymeric matrix• Low moisture resistance• Moisture absorption (up to 10-20%) which may cause

swelling problems• Low dimensional stability

Natural fibers: processability problemsThe incorporation of biofibers during compounding and subsequent transformation processes must be still optimized taking in mind the following factors :

• Variability of properties form batch to batch (see above)• Powder formation during fibers milling and subsequent

densification with consequent size variability, metering problems, clogging of the die holes with consequent pressure increase and degradation

• Tendency to create agglomerated structures during processing

• Low resistance to processing temperature. (Possible thermodegradation and yellowing above 200/220°C)

• Presence of volatile materials and water which require a very efficient venting for their elimination

• Need of careful pre-drying before processing to the fast moisture re-absorption

Biofibers

In this case there is a need of a suitable surface modification in order to improve wettability and adhesion between biofibers and polymeric matrix (mainly the apolar ones) and resistance and durability of the biocomposite.

In compounding , in order to improve adhesion, it is suggested to use compatibilizers (i.e. maleic anhydride modified polyolefines) or matrix grafted with functional groups

Biofibers vs glass fibers properties

Properties E-glass Flax Hemp Jute Ramie Kenaf Sisal Cotton

Density g/cm3

2.55 1.4 1.48 1.46 1.5 1.5 1.33 1.51

Tensile Strength* 10E N/m2

2400 800 –1500

550 -900

400 –800

500 570 600 –700

400

E-modulus GPa

73 60 - 80 70 10 - 32 44 22 38 12

Specific E 29 26 - 46 47 7 - 21 29 20 20 8

Elongation Failure %

3 1.2 –1.6

1.6 1.8 2 1.8 2 - 3 3 - 10

Moisture Absorb %

N / A 12 12 12 - 16 12 - 17 13 - 16 11 8

* Depends on the type of fiber and whether a fiber bundle or a single ultimate fiber is tested

Ref. Nova Institute, ATO, USDA, FAO, IJSG

Possibility of industrial and structural applications

Other important points for development of biopolymers in industrial and structural applications that still require further research:

• Processability , specifically in relation to their sensitivity at moisture and temperature.

• Finishing processes , such as bonding, welding, coating, painting. In many of these cases there is a need to take in account biodegradability norms.

• Ageing and durability properties . Today it is difficult to find data and information on this point.

• Study of end life of moulded parts (typically some millimeters thick). This could require creating separate recycling lines and modification of compost plants

Possibility of industrial and structural applications

Today major experiences involve PLA, since PLA, among the biopolymers available on industrial scale with an acceptable price, is the one which presents mechanical properties similar to those of traditional polymers.

PLA Properties

• Mechanical properties – Tensile strength50 – 60 MPa– Tensile modulus 3500 – 4000 MPa– Elongation 1 – 5 %– Izod 12 – 20 J/m

• Thermal properties– Tg ~ 60°C, Tm 140-180°C, Tc 95-120°C– Above 60°C tend to degrade in presence of moisture

PLA critical points

PLA critical point are:• Low thermal resistance , which could create big

problems for hot beverages, microwaves, textile ironing, and could cause part warping and deformation during transportation

• Low impact resistance which could create problems not only on moulded parts but also on film and sheet production, due to edge trimming and slitting problems

Thermal resistancePLA crystallizes very slowly, and it is very difficult to increase crystallinity level at the conventional processing conditions. As a consequence thermal resistance remain low (around 60 °C).Thermal resistance could be improved by:

• increasing crystallization rate oby using heterogeneous nucleating agent or oby using PLLA/PDLA stereocomplex as nucleating

agent for PLLA. According to Purac crystallization rate is 15-20 times faster

• by incorporation of natural fibers

PLA fibers

Recently, Teijin, one of the major world synthetic fibers manufacturers, has developed a new PLA fibers (Biofront) with a melting point much higher (210°C), by using the steroecomplex technique. It i s claimed that this fiber could be ironed and could compete not only with PP fiber but also with PET fibers.

Heterogeneous nucleating agent effect

S.Murase 2^ European Bioplastics Conference, Paris 21-22/11/2007

PLA Unitika: Terramac

ItemTest method

Unit Basic gradeTE-4000

Heat-resisting

gradeTE-7000

Heat-resisting

gradeTE-7307

Heat-resisting

gradeTE-7300

Appearance -Tran

sparentOpaque

whiteOpaque

whiteOpaque

white

Density - 1.25 1.27 1.42 1.47

Melting point °C 170 170 170 170

Breaking strength

MPa 63 70 54 54

Tensileelongation

% 4 2 2 1

Bending strength

MPa 106 110 85 98

Bending modulus

GPa 4.3 4.6 7.5 9.5

Charpy impact strength:With notch

kJ/m2 1.6 2.0 2.5 2.4

Deflection temperatureunder load of 0.45 MPa

°C 58 110 120 140

Molding shrinkage % 0.3~0.5 1.0~1.2 1.0~1.2 1.0~1.2

Fibrous reinforcement effect

T. Yanagisawa 2^ European Bioplastics Conference, Paris 21-22/11/2007

Low impact resistance

To improve PLA impact resistance, many impact modifiers have been developed.

Among the major manufacturers, it is possible to quote Arkema (Biostrength), DuPont (Biomax) e Rohm and Haas (Paraloid).

As an example data obtained by polyacrylate are reported:

Low impact resistance

B.Azimipour 2^ European Bioplastics Conference, Paris 21-22/11/2007

Impact resistance

This material allows also improvement in film and sheet slitting and trimming and present a good transparency (haze lower than 6% on 15 mil film for an additive content up to 5%) thanks to its nanometric size and excellent dispersibility.

*load 1,8MPa

% di kenaf 0 5 10 15 20 ABS

Temp inflessione sotto carico °C*

62 65 70 110 120 95

Modulo di elasticità MPa 4500 4500 5500 6500 8000 2700

Effect of natural fibers: PLA / Kenaf

Biomonomers

As already stated, the more recent market trend regards biopolymers synthesized by renewable resources monomers, even if these polymers are not biodegradable.•As a consequence, many companies are today very active with the target to realize traditional polymers, obtained by fossil resources, starting by renewable resources.•The advantage in comparison to the other biopolymers, is that they can be used without problems as a substitute for traditional material already long established on the marketSome examples:

Biomonomers • Rohm and Haas (with Ceres) : methacrylic monomers

by bioethanol (PMMA for sheet, coating, paints). • Cargyll (with Novozymes) : acrylic acid by 3-

hydroxypropionic acid (3HPA) obtained by sugar fermentation (for production of fibers, plastics, varnishes).

• Braskem (Brazil) : ethylene from sugarcane (200000 t/year plant by the end of 2009).

• Dow ( jv with Crystalsev ) ethylene by ethanol in Brazil. (350000 t/year plant by the end of 2011)

• Solvay ethylene by ethanol in Brazil for the production of bio-PVC. (Forecasted to be 60000 t/year plant)

Biomonomers

• DuPont: 1,3 propanediol, key ingredient for biopolyester and liquid polyols in a j.v. with Tate&Lyle ,a major corn-based products Company with expertise in fermentation processes. A plant of 45.000 ton capacity is under construction

•Bayer: a polyol, intermediate for PU, by vegetable oils and monosaccharide compounds. According to Bayer this material presents a potential market growth to 1000 kTon/year by 2015 and a cost advantage up o about 0.2 Euro/kg (based upon current cost differences)

Proplast , with its large experience in compounding and product and process engineering is interested and available to co-operate with companies interested in developing biopolymers new formulation and application of biopolymers .

www.proplast.it

proplast@proplast.it

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