BIOPOLYMERS

Market and technological new

trends

Members

113 Enterprises
8 Industrial associations
3 Foundations and public bodies
14 Universities
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.

Politecnico di Torino
Universit Piemonte Orientale
Universit di Genova
Universit di Pisa
Universit di Palermo
Universit di Salerno
Universit di Modena e Reggio Emilia
Universit di Napoli
Universit di Torino
Universit di Messina
ICIMSI Supsi (Svizzera)
Universit di Milano
Universit di Camerino
Universit degli studi di Brescia

138 members

Research on Materials

Nanocomposite materials (POSS, nanoclay, nanotubes, etc.)

Recycling
Improvement of properties (fire retardancy, mechanical,
barrier, physical, weathering, thermal degradation, etc.)
Biopolymers (compounding and processing)

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.
2.

Optimization of parts manufacturing;

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 area

As 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-based
synthetic
Microbial
synthesized
Aliphatic
polyesters

Polylactic acid, PLA

Starch plastics
Cellulosic plastic
Soy-based plastic

Polyhydroxy
alkanoates, PHA
Polyhydroxybutyrate
co-valerate, PHBV

Aliphaticaromatic
polyesters
Polyesteramides

Petro-Bio
(Mixed) Sources

PTT
Biobased
Polyurethane
Biobased
epoxy
Blends etc

Polyvinyl
alcohols

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
processes
are 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
applications

or

structural

(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
natural sources or biodegradable which can
incorporated into biopolymers.

by
be

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 Commissions 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
Biodegradation Standard
Aerobics test
in aqueous medium
CO2
convertion
ISO 14852

Anaerobics test

solid

in aqueous medium
ISO 14853

O2
consumption
ISO 14851
Compost
ISO 14855

CO2
production

In soil or landfill
ISO 17556

Mineral bed
omposting
ISO 14855 emenda

High solid
ISO 15985

Standard
In selecting additives in order to develop formulations that will
allow tailoring biopolymers for specific application, it will be
necessary 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, Vinotte,
ecc)

Bioadditive - examples
Clariant 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.

Biofibers
In 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 problems

The 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 200/220C)
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

Elongation
Failure %

1.2
1.6

1.6

1.8

1.8

2-3

3 - 10

Moisture
Absorb %

N/A

12

12

12 - 16

12 - 17

13 - 16

11

* 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 ~ 60C, Tm 140-180C, Tc 95-120C
Above 60C 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 resistance
PLA 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
o by using heterogeneous nucleating agent or
o by 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
(210C), 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

Heatresisting
grade
TE-7000

Heatresisting
grade
TE-7307

Heatresisting
grade
TE-7300

Tran
sparent

Opaque
white

Opaque
white

Opaque
white

1.25

1.27

1.42

1.47

170

170

170

170

MPa

63

70

54

54

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
temperature
under
load of 0.45 MPa

58

110

120

140

Molding shrinkage

0.3~0.5

1.0~1.2

1.0~1.2

1.0~1.2

Item
Test method

Unit

Appearance

Density
Melting point
Breaking
strength
Tensile
elongation

Basic grade
TE-4000

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.

Effect of natural fibers: PLA / Kenaf

% di kenaf

10

15

20

ABS

Temp inflessione
sotto carico C*

62

65

70

110

120

95

Modulo di
elasticit MPa

4500

4500

5500

6500

8000

2700

*load 1,8MPa

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 market
Some examples:

Biomonomers
Rohm and Haas (with Ceres) : methacrylic monomers
by bioethanol (PMMA for sheet, coating, paints).
Cargyll (with Novozymes) : acrylic acid by 3hydroxypropionic 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 cornbased 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 cooperate with companies interested in developing
biopolymers new formulation and application of
biopolymers .

www.proplast.it
[email protected]

Grazie per la vostra

attenzione