New solutions in biopolymers for food and cosmetic industry
Biopolymers:
general concepts
What is a
Biopolymer?
Why bio?
The prefix bio is used in the world of polymers to define its
natural, vegetable or animal origin.
Also is used to indicate the biodegradability of the polymer.
A Biobased polymer originates wholly or partly in biological
material including trees, crops, grasses, algae and vegetable
waste.
Biobased content is determined by the method of Carbon 14 (CEN
/ TS 16137 ASTM‐6866) which determines the ratio of C‐14 in the
C total.
Biodegradable Plastics
Plastic materials wich under certain environmental conditions, with the help of living organisms degrade, becoming completely natural elements: carbon dioxide, water and compost. Biodegradable plastics can have natural origin, biobased, or produced from fossil resources.
Bioplastic
It is a plastic that is made from natural raw materials (such as sugar,
starch, cellulose, potatoes, cereals, molasses, soybean oil, corn, etc.)
it is made in a sustainable way, it is biobased; and it may or may not
be biodegradable.
Compostable
A material is compostable when it biodegrades within a certain time under specific conditions that define composting. Composting is a procedure carried out by humans advancing the natural processes of biological decomposition and gives products like carbon dioxide, water, and mineral fertilizer (compost). A compostable material, by definition, is biodegradable, but a compostable material is not necessarily biodegradable. Should be met with European standard EN 13432 (US ASTM D6400‐04), decomposition of 90% or greater in less than 6 months.
Types of composting
Domestic composting is being performed at room temperature with moisture and microorganisms. It can be done al home.
Industrial composting is being carried out at elevated temperature (50‐70⁰C), high humidity and microorganisms. It is the composting of residual urban organic matter (brown container in Catalonia and the Basque Country).
Oxo‐degradables plastic
Oxo‐degradable plastics are conventional plastics (generally PE) to which additives have been added. These additives function as catalysts in order to decompose the plastics by the action of light, heat or UV (photodegradable) The material does not degrade, it just breaks into smaller fragments. The material does not meet the standards of composting.
The EU has recommended to its member states the total ban of oxo‐degradable plastics by 2018.
Sustainability: A situation or a feature by which the needs of
the current population can be met without compromising the
ability of future generations or people from elsewhere (UNEP).
Life Cycle: Are consecutive and interconnected stages of a
product from obtaining‐production to its end of life in landfills
or incineration, through its manufacture and use in their
lifetime (ISO 14044).
Life Cycle Assessment (LCA): It is the collection and evaluation
of the inputs, outputs and the potential environmental impacts
of a product system throughout its life cycle (ISO 14044).
Carbon footprint: It is the addition of emissions of greenhouse
gases, expressed as carbon dioxide equivalent, in a system
based on an analysis of product life cycle (ISO 14067).
Biopolymers
Bio Origin
•BIO PE
•BIO PU
•BIO PA
•BIO PVC
•Starch
•Cellulose
•Cellophane
•PLA
•PHA
Bio Origin
Bio Origin
+
+
Non Biodegradable
Biodegradable
Petrochemical
+
•PE,PP,PS
•ABS, PC, PMMA
•PUR
•PA
•PET
Non
Biodegradable
Petrochemical
+
Biodegradable
Biodegradability
•PCL
•PBAT
•PBS
•PVOH/PVA
•PGA
Biodegradable Polymers
Biodegradable
Polymers
Biopolymers from renewable sources Biopolymers from non‐renewable sources
Bioplastics
Polymer extracted from biomass:
starch, cellulose,
lignin, proteins
Synthesized from de biomonomers
Produced from microorganisms
PLA
PHA
PBS: polybutylene polysuccinate
PBSA: Poly (succinate‐co‐butylene adipate)
PCL: Polycaprolactone
PHA: polyhydroxyalkanoates
PLA: polylactic acid
Petrochemical origin
PCL, PBSA, PBS Other biopolymers, wholly or partially from biological origin, but non‐biodegradable:
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PET: 30% MEG (via fermentation) + 70% PTA (petrochemical origin).
PE: ethylene (via fermentation).
PTT: 1,3 propanediol (via fermentation) + PTA (petrochemical origin).
PBT: 1,4 butanediol (via fermentation) + PTA (petrochemical origin).
PUR: polydiol (via fermentation) + isocyanate (petrochemical origin).
PA6: caprolactam (via fermentation).
PA66: adipic acid (via fermentation) and hexamethylenediamine (petrochemical).
PA69: chemical transformation of oleic acid.
Other.
Carbon footprint Comparison of different polymers
Emissions from the production of common polymers
(kg. CO2 eq. per kg. of polymer‐ from cradle to factory gate)
Source: Plastics Europe (http://www.plasticseurope.org/plastics‐sustainability/eco‐profiles.aspx). 2006
Life cycle of biodegradable bioplastics
Compounds based on aliphatic polyesters biopolymers:
ErcrosBioPH: Products based on PHA
ErcrosBioL: Products based on PLA
ErcrosBio PH
General Characteristics
Compounds bases on PHA
There are aliphatic polyester made directly by lips or sugars fermentation by
bacteria, with a chemical structure as follows:
There are around of 150 different PHA :
Homopolymers:
 PHB :R= CH3‐
 PHV :R= CH3‐CH2‐
 PHH :R= CH3‐CH2‐CH2‐
Copolymers:
 PHBV ó P(3HB‐co‐3HV)  PHBH ó P(3HB‐co‐3HH) ErcrosBio PH
Applications
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Packaging for food and non food end use.
Films: waste bags
One use cutlery.
Textile uses.
High degradability products.
Other: PVC plasticizers.
ErcrosBio PH
ErcrosBio PH 070
ErcrosBio PH 110
ErcrosBio
PH 070
ErcrosBio
PH 110
Units
1
2
g/10 min
Propiedad
Método
Melt Flow Index (M.F.I.)
ISO 1133 (160ºC, 2,16 Kg)
Density
ISO 1183
1,21
1,20
g/cc
Melting Temperature (Tm)
DSC: ISO 11357
141
126
ºC
Glass Trans.T emperature (Tg)
DSC: ISO 11357
‐1
‐3
ºC
Thermal propertiers
TGA (método propio)
272
270
ºC
ErcrosBio PH
Pros
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Depending on PHA characteristics, different properties.
Mechanical properties similar than olefins (~LDPE ).
No catalyzers traces.
Good barrier properties similar to aromatic polyester (~ PET). Good fat and solvents resistance.
Buena for blowing process.
Good hydrolysis stability. Cons
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Low temperature processability. Process not easy.
Brittle in some cases.
Low viscosity.
Additives incorporation
New products development
ErcrosBio L
General Characteristics:
Grades in PLA:
* LL600
* LL650
* LL700
* LD600
ErcrosBio L
Applications
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Packaging for food and non food end use.
Construction for foaming, profile, siding,…
One use cutlery
Textiles uses
Electric and electronic end use.
Automotive
ErcrosBio L
Pros:
•
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Sustainable origin made from natural sources.
Compostable and burnable.
Mechanical properties similar than PET y al PS.
Printable.
Water and fatty product resistance.
Sealable at lower temperature than olefins.
High Young modulus.
Transparent.
Similar olefin process (extrusion, injection and thermoforming).
Cons:
•
•
•
High risk of hydrolysis.
Low Permeability.
Stiffness.
ErcrosBio L
ErcrosBio LL600, ErcrosBio LL650, EcrosBio LL700
80
3,5
70
3
Modulo de Young (GPa)
60
50
40
30
2,5
2
1,5
1
20
0,5
10
0
0
ErcrosBio LL 600
ErcrosBio LL 650
ErcrosBio LL 700
ErcrosBio LL 600
ErcrosBio LL 650
ErcrosBio LL 700
6
5
ErcrosBio LL700 very rigid material
Elongacion a rotura (%)
Esfuerzo en el punto de fluencia (MPa)
Mechanical properties
4
3
2
1
0
ErcrosBio LL 600
ErcrosBio LL 650
ErcrosBio LL 700
ErcrosBio L
ErcrosBio LL600, ErcrosBio LL650, EcrosBio LL700
Injection
Melt Flox Index 190ºC, 2.16Kg (g/10min)
12
10
8
6
4
Extrusion
2
0
ErcrosBio LL 600
ErcrosBio LL 650
ErcrosBio LL 700
40
20
35
Transmision al O2 OTR
23ºC 0% humedad (cc/m2.d)
Transmision vapor de agua WTR
38ºC 90% humedad (cc/m2 d)
18
16
14
12
10
8
30
25
20
15
6
10
4
5
2
0
0
ErcrosBio LL 600
ErcrosBio LL 650
ErcrosBio LL 700
ErcrosBio LL 600
ErcrosBio LL 650
ErcrosBio LL 700
ErcrosBio L
ErcrosBio LL600, ErcrosBio LL650, EcrosBio LL700
Properties to be modified:
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Oxygen and water vapor permeability.
Thermal properties.
Stiffness.
Additives incorporation
New products development
ErcrosBio LM
LM
Transparent extrusion grades Opaque extrusion grades Transparent injection grades
Opaque injection grades
72000 series
73000 series
62000 series 63000 series ErcrosBio LM Aditives 73000 Series PLA pellets
Extruder
Dry PLA Drying
Extruder
Drying
PLA Films and sheets
Thermoformed products
ErcrosBio LM 73000 Series 4
70
3,5
60
3
Modulo de Young (GPa)
80
50
40
30
2,5
2
1,5
20
1
10
0,5
0
0
ErcrosBio LL700
ErcrosBio LM 73101
ErcrosBio LM 73501
ErcrosBio LM 73501 higher tenacity to deformation
> 100%
ErcrosBio LL700
ErcrosBio LM 73101
ErcrosBio LL700
ErcrosBio LM 73101
ErcrosBio LM 73501
120
100
Elongacion a rotura (%)
Esfuerzo en el punto de fluencia (MPa)
Mechanical properties
80
60
40
20
0
ErcrosBio LM 73501
ErcrosBio LM 73000 Series 6,0
Improvement in pearmeabilty in oxigen and water vapor
5,0
4,0
3,0
2,0
1,0
0,0
ErcrosBio LL700
ErcrosBio LM 73101
ErcrosBio LM 73501
40
25
Transmision al O2 OTR
23ºC 0% humedad (cc/m2.d)
35
Transmision vapor de agua WTR
38ºC 90% humedad (cc/m2 d)
Melt Flox Index 190ºC, 2.16Kg (g/10min)
7,0
22 %
20
15
10
22 %
32 %
30
25
20
15
10
5
5
0
0
ErcrosBio LL700
ErcrosBio LM 73101
ErcrosBio LM 73501
ErcrosBio LL700
ErcrosBio LM 73101
ErcrosBio LM 73501
ErcrosBio LM 60000
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Range of products for the production of components by injection molding and blow injection molding
Transparent products: Series 62000 Opaque products: Series 63000
ErcrosBio LM
Aditives Extruder
63000 Series PLA Pellets
Drying
Injecction
Dry PLA Drying
PLA End products
ErcrosBio LM
63000 Series 70
4
60
3,5
3
50
Modulo de Young (GPa)
Esfuerzo en punto de fluencia (MPa)
Mechanical properties
40
30
2,5
2
1,5
20
1
10
0,5
0
0
ErcrosBio
LL650
ErcrosBio LM
63101
ErcrosBio LM
63102
ErcrosBio LM
63103
ErcrosBio LM
63104
ErcrosBio
LL650
ErcrosBio LM
63101
ErcrosBio LM
63102
ErcrosBio LM
63103
ErcrosBio LM
63104
ErcrosBio
LL650
ErcrosBio LM
63101
ErcrosBio LM
63102
ErcrosBio LM
63103
ErcrosBio LM
63104
160
140
Elongacion a rotura (%)
ErcrosBio® LM 63103 y 63104 high tenacity materials with breaking deformation > 140%, with modulus similar than standard PLA.
120
100
80
60
40
20
0
ErcrosBio LM
63000 Series Melt Flox Index 190ºC, 2.16Kg (g/10min)
10,0
9,0
8,0
7,0
Improvement in permeability properties in oxygen and water vapor.
6,0
5,0
4,0
3,0
2,0
1,0
0,0
ErcrosBio
LL650
ErcrosBio LM
63101
ErcrosBio LM
63102
ErcrosBio LM
63103
ErcrosBio LM
63104
45
3%
20
14 %
18
21 %
35
27 %
53 %
30
25
20
15
10
Transmision vapor de agua WTR
38ºC 90% humedad (cc/m2 d)
Transmision al O2 OTR
23ºC 0% humedad (cc/m2.d)
40
19 %
30 %
16
14
12
10
8
6
4
5
2
0
ErcrosBio
LL650
ErcrosBio LM
63101
ErcrosBio LM
63102
ErcrosBio LM
63103
ErcrosBio LM
63104
0
ErcrosBio
LL650
ErcrosBio LM
63101
ErcrosBio LM
63102
ErcrosBio LM
63103
ErcrosBio LM
63104
CONCLUSIONS  Ercros has a range of products based on PLA.
 With a variety of properties specifically tailored to meet the requirements for processing and to have required properties.
 Application for extrusion and extrusion‐
thermoforming, injection and injection blow molding
 To obtain a wide variety of finished products.
Thanks for your interest!
Belén Pascual, head of R&D in plastic division. [email protected]
Domingo Font, biopolymers sales manager
[email protected]