Bio Plastics

7/18/2019 Bio Plastics

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Bioplastics

plastics of the future ?

Dr Jérôme Peydecastaing

May 2013

The context



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Global demand for plastics

in 2011: 205 million tonnes (BPF)

“Traditional” plastics are:

Recyclable

Versatile

Lightweight

Moisture resistant

Durable

Strong

Relatively inexpensive

It can be chemical resistant, clear or opaque.

These are wonderful useful qualities, and plastic

plays many important roles in life.



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But “Traditional” plastics are also:

Derived from non-renewable, fossil sources.

Responsible for global warming when burned.

Non-biodegradable, tend to accumulate.

Responsible for pollution: To be recycle, plastics have to be

collected.

Recycling



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Recycling

Source: Wrap

Non-Biodegradability of plastics

600-1000 years?



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In this context

Renewable resources are becoming a more viableand promising alternative for the plastics industry.

What about biodegradable plastics ?

R&D activities on

“bioplastics”

Ideal scenario and marketing



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Definitions

Definitions

Bio-based material:

• an engineering material made from substances derived fromliving matter. ( !"#$ &'('' )

Biopolymer:

• any polymeric chemical manufactured by a living organism,

as proteins and polysaccharides.• such a chemical prepared by laboratory synthesis.

Bioplastics:

• The term "bioplastics" refers to a biodegradable plastics and/

or plastics derived from renewable resources (the definitionfrom European Bioplastics)



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Thermoplastics and thermosets

Thermoplastic Thermoset

Temperature

Rubbery state

Glassy state

Tg

Transitionarea

Tg: glass transitiontemperatureLow molecular

agitation

breakablepolymer

High molecularagitation

Thermoplasticity



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Thermoplastics and thermosets

The bioplastics



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Bioplastics

Natural polymers from biomass (starch, modified

cellulose).

Polymers obtained by microbial production (PHA).

Synthetic polymers whose monomers are obtained from

biomass (PLA).

Synthetic polymers whose monomers and polymers areobtained conventionally by chemical synthesis (PCL,

aliphatic and aromatic copolyesters).

Overview of bio-derived feedstock and polymers

Natural polymers Synthetic polymers



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Natural polymers

Agricultural feedstock

Natural polymers: Starch

Second largest biomass on earth, after cellulose

The predominant food reserve substance in plants

where it occurs as starch granules

• Seeds (e.g. peas, grains, beans)

• Roots, tubers, stems (e.g. potato, tapioca, pineapple)

• Fruits (e.g. plantain bananas)

• Leaves (e.g. tobacco)

One of our main carbohydrate source

Primary use in foods



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Natural polymers: Starch (C6H10O5)n

Starch is complex made of polysaccharides whose repeatingglucose units are linked by !1!4 glycosidic linkage.

The length of the starch chain will vary between 500-20,000glucose units.

There are actually two types of starch molecules:

• Amylose

• Amylopectin.


Amylose

Amylopectin

Starch



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MILLING

STARCH

AMORPHOUS

AMYLOSE AND

AMYLOPECTINE

COMPLEXED

STARCH

Destructuration

Chemical modification

POLYMERIC

COMPLEXING AGENTS

Cereals, tubers, !

Final product

Emerging application areas

! COATED PAPER ! AGRICULTURE MULCH FILM ! SHOPPING BAGS

! FOOD WASTE FILMS AND BAGS

! CONSUMER PACKAGING MATERIALS ! LANDFILL COVER FILMS ! OTHER APPLICATIONS




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Natural polymers: Cellulose

Natural polymers: Cellulose

Why modify cellulose ?

Amorphous region Crystalline region

O

OH

OH

HO

O

OH

HO

OH

O

Cellulose is not a thermoplastic

( ! -1,4-glycosidic linkage)



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Natural polymers: Cellulose acetate

Raw materials:

• Wood pulp: high-quality (>95% !-cellulose and1000<DP<2500)

• Cotton : high purity raw material with !-cellulose content

(>99%) and 1000<DP<7000

Cellulose acetate:

1865


Two categories of processes :

> Acetylation in homogeneous system

• glacial acetic acid

• methylene chloride

> Acetylation in heteregeneous system

• CCl4

• Toluene



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Thermoplastic materials.

Transparency, high clarity.

Toughness.

Moisture resistance.

Dimensional stability.

Slowness to burn.

Non Biodegradable.

Natural polymers: Cellulose esters

Thermoplasticity



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Natural polymers: New concept

Natural polymers

Microbial origine



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Bacterial bioplastics: PHAs

Polyesters accumulated inside microbial cells ascarbon & energy source storage.

PHA: White patches in microorganism


Produced under conditions of Low limiting nutrients (P, S, N, O) andExcess carbon.

~250 different bacteria have been found to produce some form ofPHAs.

PHA RPHB - CH3

PHV -CH2CH3

PHBV (Biopol®) - CH3 & CH2CH3

PHBHx -CH3 & - CH2CH2CH3

PHBO -CH3 & -(CH2)4CH3

O

R

OH

O

H

x

n

PHA structure

R = Hydrocarbon (up to C13)x = 1 to 3 or moreN = 100 – 30 000



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Bacterial bioplastics: Recovery of PHA

PHA producing microorganisms stained with Sudan

black or Nile blue

Cells separated out by centrifugation or filtration

PHA is recovered using solvents (chloroform) to

break cell wall & extract polymer

Purification of polymer


Advantages

" Biodegradable

" Eco-friendly synthesis

" Renewable resource

" Good mechanicalproperties

" Water resistant

Inconvenients

" Poor interaction withfibers

" Extraction process

" Narrow processingwindow

" Thermal degradation(185°C)

" Brittleness



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Bacterial bioplastics: PHB

Discovered by Frenchmicrobiologist Maurice

Lemoigne in 1923.

Next generation PHB will

come from Transgenic

plants/micro-organismsTypical cost ranges from

5-6 "/kg Ref: Marchessualt, R. H.; TRIP, 1994, 4, 163

Synthetic polymers

Biotechnological origin



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PLA is not a polyacid,

but rather a polyester

Polylactic acid (PLA)

PLA are thermoplastic aliphatic polyester made from

!-hydroxy acids, derived from renewable resources, such as:

• corn starch (in USA),

• tapioca products (roots, chips or starch mostly in Asia),

• sugarcanes (in the rest of world).

Catalyzer: Stannous octonate or tin(II) chloride


Bacterial fermentation is used to produce lactic acid.

Two lactic acid molecules undergo a single esterfication andthen catalytically cyclized to make a cyclic lactide ester.

PLA of high molecular weight is produced from the dilactate

ester by ring-opening polymerization.



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Lactic Acid

Fermentation

Unrefined Dextrose

PolymerProduction PLA

MonomerProduction

Lactide

Corn Starch

SugarProduction

PLA Manufacturing Overview

PLA rigid Packaging

Sources: Novamont; Coopbox; Whole Foods Market; NatureWorksTM

Low glass transition

temperature

PLA materials cannot

hold hot liquids.

However, much

research is devoted to

developing a heat

resistant PLA



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PLA is biodegradable (short-term packaging) and

biocompatible (biomedical applications).

Good mechanical properties (can be comparable to PET)

PLA can be degraded by abiotic degradation. In a second

step, the enzymes degrade the residual oligomers till final

mineralization.

PLA is an environmentally friendly material when lactic acidis produced from biomass by fermentation,.

PLA production leads to a growing demand for corn,

competing bioethanol production and corn-dependent

commodities.

Synthetic polymers

Petroleum / natural based



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Fossil-based bioplastics

Synthetic biodegradable polymers whose monomers and

polymers are obtained conventionally by chemical synthesis.

Less than 1% of the bioplastics in 2011.

Polycaprolactone (PCL) Polyesteramide (PEA)

Aliphatic copolyesters (PBS) Aromatic copolyesters (PBT)

Bio-based synthetic plastics

Synthetic polymers non biodegradable usuallyobtained from fossil resources.

They are considered as bioplastics when derived

from renewable resources.

Polyethylene

PE

Polyvinyl chloridePVC

!

Polypropylene

PP



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Bark of pine, corn sheets, orange peels, potato skins, oats# othernonfood resources

Biological and chemical process

PET (identical to fossil sourced)

Experimental production in 2012

PepsiCo

A bottle 100% bio-based

Biorefineries of the future will integrate:

Production

End-Uses

Products – Fuels

– Plastics

– Solvents – Chemical Intermediates

– Phenolics

– Adhesives

– Hydraulic Fluids

– Fatty acids – Carbon black

– Paints – Dyes, Pigments, and Ink

– Detergents

– Pulp & Paper products – Horticultural products

– Fiber boards

– Solvents

– Adhesives – Plastic filler

– Abrasives

Fuel

Power

Processing

- Acid/enzymatic- hydrolysis

- Fermentation

- Bioconversion

- Chemical Conversion

- Gasification- Combustion

- Pulping

Plant Science

- Wood, trees- Grasses

- Energy crops

- Agricultural

Residues

- Genomics- Enzymes

- Metabolism

- Composition



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Biodegradability

Concept



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Definitions

Biodegradation: degradation caused by the action of

microorganisms (3 steps):

• Biofragmentation of the material

• Bioassimilation

• mineralisation in CO2, H2O and/or CH4 and a new biomass

A material is called biodegradable with respect to specific

environmental conditions if it undergoes biodegradation to aspecified extent, within a given time, measured by standard

test methods.

• Compostable plastic is one that meets all scientifically

recognized standards of compostabilty regardless of the origin of

carbon.

• Compostable plastic is always biodegradable

• Biodegradable plastic is not always compostable

What is compostable plastic?

European standard is EN 13432,USA standard is ASTM D6400.



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Macroscopic and microscopic scales

Photodegradable plastics can break down to small fragments and lose

structure but small fragments are not degradable.

Semidegradable plastics often contain starch, cellulose and polyethylene.

Dramactic impact on the planet

ASTM D6400 – Main Factors

1. Mineralization

> 90 percent conversion to carbon dioxide, waterand biomass through the action of microorganisms

> The same rate of degradation as other organicwaste (ie. leaves, grass ...)

> Time period of 180 days or less

2. Fragmentation> Not more than 10% of the original dry weight of test material shall

fail to pass through a 2 mm fraction sieve.

3. The impact on the environment

> No negative impact on flora and fauna



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ISO

(Global)

JIS

(Japan)

ASTM

(USA)

CEN

(UE + AELE)

AFNOR(France)

DIN(Germany)

BS (UK) #.

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New ISO 17088 for compostable plastics (2012)

So many Standards

• 2 major axis of studies:

- measurement in simulated environment (laboratory tests)

- measurement in real environment

Sturm test / Enzyme

assay / Clear-zone test

Mixed culturesDefined media

Soil / Compost

Landfill / Water

Externalconditions

Laboratorytest systems

Field

tests

Simulationtests

Definedconditions

Transferability to practice

Analytical accessibility

Soil / Compost

Landfill / Water

The assessment of biodegradability



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Pressurized air Air (no CO2) Air outlet

Plastic

+ liquid

O2consumptionmeasurement

Titration

Gas chromatographyFTIR or NIR

Clean air (no CO2)

producer

Fermenter Measurement system

Plastic

+ liquid

CO2 productionmeasurement

Laboratory tests

0

100

200

0 5 10 15 20 25 30 35 40 45

Time (Days)

T o t a l C O 2 p

r o d u c t i o n ( g

Cellulose

Blank - Inoculum

= net CO2 production

= biodegradation

EN 13432: Biodegradability



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Bioplastics and biodegradability

Generally accepted ideas

Bioplastics are biodegradable

Petrochemical plastics are not biodegradable

Bioplastics and biodegradability

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Bioplastics market



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I/J/45DH/06 5G 375D42;<=; 6K.5C9K K7;65.L

Renewable resources

Petrochemical raw materials

DegradableNon-

degradable

Based onrenewable

resources

Bio-degradable

V.BioPE, BioPA

BioPU, BioPP, BioPVC

I.Cellulose acetate

Rubber #

IV.Starch blends

PHA

PLA

Regenerated cellulose

#

III.Polycaprolactone

Polyvinyl alcohols

Polyesters

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II.Polyethylene

Polypropylene

Polyvynil chloride

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Projected Bioplastics trends

Production capacity of bio-based plastics is projected to increase

from 360,000 tonnes in 2007 to about 2.3 MILLION tonnes by 2013.(European Bioplastics)

Global production capacity for PLA (Polylactic Acid) is expected to be

800,000 tonnes by 2020. (Nova Institute 2012)

USA demand for bioplastics predicted to grow at 20% through 2016

to reach 249,000 tonnes valued at "552 million. (Freedonia Group 2012)

Biodegradable account for the majority of bioplastics in 2011 but non-

biodegradable will grow to 40% of the market by 2021.

Major growth will be bio-based Polyethylene as well as bio-based

PET and PVC.



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European Union

Plastics: 57 M tons

100% from biomass

34% Europe lands limagrain

Non food biomass (Food waste) has to be used for bioplasticcs.

Compostable Bioplastics Do Not Yet

meet the Needs for Durables

Starch Blends

Hydrolytic stability

Distortion Temp

Vapor Transmission

Shelf Life

PLA

Hydrolytic Stability

Distortion Temp

(amorphous)

Vapor Transmission

Shelf Life

Impact Resistance

Melt Strength

PHA S

Hydrolytic Stability

Shelf Life

Processability

Melt Strength

Economics

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BraskemDow/Crystalsev

DuPont Arkema

BASFRohm & Haas

Dow, Cargill

NatureWorks LLC

HDPE, LLDPE, PPHDPE

NylonNylon

Nylon Acrylics

Soy based urethanes

PLA Blends

Degradable

Durable

NovamontNatureWorks

MetabolixDSM

Origo (starch)PLA

PHA’sPHA’S

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########################################## WHO? WHAT?

Biobased Leaders Tomorrow?

Cost (2010) Leaders Commercial products

1,5-3 " /kgStarch

# NOVAMONT # RODENBURG # NATIONAL STARCH # BIOTEC

# Mater-Bi

# Solanyl

# Ecofoam

5-6 " /kg **

3-4 " /kg PLA

PHA

# CARGILL # Nature Works

# METABOLIX # PROCTER&GAMBLE

# Biopol

# Nodax

# BASF # EcoFlex Poyester

Traditional plastics cost (PE, PP, PVC...)

1 " /kg

3-5 " /kg **



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The future for bioplastics will depend on!.

Expanding from Single Use Compostable to Durable

Applications

Focus on Life Cycle Assessment

Transitioning from Oil Based to Renewable Feedstock

Addressing Issues – Sociological, Environmental & Political

Composting/Recycling Infrastructure Developments

What about modified bio-materials ?

[email protected]

www.chimieagroindustrielle.fr

Thank you for your attention

Any questions ?



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Bio Plastics

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