“biodegradable and biobased

Internal

“Biodegradable and biobased

polymers”Andreas Künkel

Uni Kassel

Kassel, Germany (digital meeting)

June, 2021

13C / (12C + 13C) (%)

13C atom percent

Internal

Introduction

Andreas Künkel

2

19692021

School Social

service

88-901975-88

University

Marburg

Biology

MPI

Marburg

Ph. D.

1990-95 95-98

BASF

Biotech

research

Marketing

Fine

Chemicals

Marketing

Biodegradable

Polymers

Research

Biopolymers

1999-2003 2003-2006 2006-2010 since 2010

Internal

Actual market development

The origins of polymer development

3

Pioneering work for polymer structure and synthesis of materials

Herrmann Franz Mark

3.5.1895 – 6.4.1992

BASF 1927 - 1932

From: University of Vienna

Internal

Rethinking Plastics

Today’s plastic economy is far from being sustainable

4

➔ Only 14% of the 78 million t annual

production of plastic packaging is collected

for recycling

➔ Insignificant 2% are recycled cradle-to-

cradle, 72% are not recovered at all

(landfilling, littering)

➔ Current status: 95% loss of material value

(80-120 billion USD) after first use plus

significant external costs caused by material

leakage to the environment and green house

gas emission (est. 40 billion USD annually)

June 29, 2021

Source: Ellen McArthur Foundation

Internal

Actual market development

Increasing global discussions about the end of life of polymeric materials

5

Stakeholders ask the question: “What to do?” and “Are biodegradable

materials a truly sustainable alternative?”

Plastics in marine

environment

Microplastic discussion

2014 2050

Ratio of Plastics to Fish in the Ocean (Ellen

MacArthur Foundation, The new plastics economy,

2016)

Internal

Use in City

Organic waste management

Food production

Biodegradation

The circular economy vision with use of biodegradable and biobased materials –

how to close the nutrient loops

PackagingMulch Films Bags

➔ Biodegradable polymers as enabler for

organic waste recycling and closing the loop

– case study e.g. Milan (Italy)

Internal

Polyester / Compounds

BASF provides biodegradable and biobased polymer solutions for bags, packaging

and agro applications

June 29, 20217

ecovio® F Mulch

ecovio® F Filmecovio® Flexible packaging

ecovio® FS Paper

ecovio® Rigid packaging

Film Applications

Packaging

Solutions

ecovio® EA Foam

Packaging

ecovio® F Film

Internal

Introduction

Definition of biobased and biodegradable

8 June 29, 2021

➔ Biobased (renewable)

refers to the origin of the

carbon atoms in the

polymers

➔ Biodegradation by

microorganisms is a matter

of polymer structure, not of

carbon origin

Non-

biodegradableBiodegradable

Biobased raw materials

Biodegradablepolyester

(e.g. ecoflex®)

compounds(e.g. ecoflex® /

PLA)

PLA

PE

Bio-PE

PHA

Starch

Cellulose

Polyamide

5,10

Polyamide

6,6

Fossil raw materials

Internal


ecoflex® as modular system

June 29, 20219

Terephthalic acidAdipic acidSuccinic acid1,4-Butanediol

Melt polycondensation

PBAT

(ecoflex®)XXYY XX+ +PBST

XX

◼ ecoflex® is a random aliphatic-aromatic copolyester

◼ Access to biobased ecoflex® variants possible (e.g. by replacing adipic acid with biobased succinic acid)

◼ Each monomer change influences melting point, tensile strength, crystallization speed & biodegradation behavior

Change of monomer and monomers composition results in new properties

Internal


Compounds of ecoflex® and other polymers (starch, PLA, PHA)

results in different property profiles

June 29, 202110

ecoflex®

PLA PHAs

Starch

Internal


Limits of classical melt polycondensation for biodegradable polyesters

June 29, 202111

Accessible property region for

biodegradable polyesters made

by classical melt polycondensation

non-biodegradable

Polymers

biodegradable

Polyester➔Compounds needed for broader

property range

➔ ecovio® is the trade name for BASF’s ecoflex® – PLA compounds

Elongation @ break (%)0

1.000

2.000

3.000

4.000

0 200 400 600 800 1.000

ecoflex

(PBAT)

Poly lactic acid (PLA)

PS

PP

HDPE

LDPE

Polybutylen-

succinate

(PBS)

E-Modulus （MPa）

PBT

Polyhydroxybutyrate (PHB)

ecovio®

Aonilex

(X151A)

Internal

Packaging – coffee capsules

Coffee: past and present

June 29, 202112

1908 2006

//commons.wikimedia.org/wiki/File:Kaffeefilter.jpg

//commons.wikimedia.org/wiki/File:Nespresso-Kapseln.jpg

Internal


ecovio®, biodegradable coffee capsules

June 29, 202113

Coffee consumption in Germany: citizen/day

Compostable

Used coffee

capsule contain 70

wt-% of water

Missing

property

High variety of hot drinks easily

prepareable via capsules

➔ To use coffee grounds

as composting

material, degradable

capsules are required

Plastic waste

http://www.google.com/url?sa=i&rct=j&q=&esrc=s&frm=1&source=images&cd=&cad=rja&docid=5lqXiWYGkF6GiM&tbnid=z4OK5WoyTmVgMM:&ved=0CAUQjRw&url=http://www.einslive.de/magazin/extras/2011/07/110711_personalisierung_google.jsp&ei=v3_mUrKsCNC20QXW34CgDA&bvm=bv.59930103,d.bGE&psig=AFQjCNGe4ojCa9GsQ1SsLPCRXPq2Z-NC5w&ust=1390924080769436

http://www.google.com/url?sa=i&rct=j&q=&esrc=s&frm=1&source=images&cd=&cad=rja&docid=FBxI_bQPO7TSWM&tbnid=Xq1PXUc8LyV46M:&ved=0CAUQjRw&url=http://www.kapsel-kaffee.net/der-inhalt-der-kaffeekapseln-im-vergleich-was-steckt-drin/&ei=-oDmUqmRMeme0QWJjoCwDA&psig=AFQjCNH_jiUkveCPQ-xSKoidNZI6I4vjzA&ust=1390924164007264

http://www.google.com/url?sa=i&rct=j&q=&esrc=s&frm=1&source=images&cd=&cad=rja&docid=cxaWCsrO3UjzmM&tbnid=AyoUhe2yVQeuGM:&ved=0CAUQjRw&url=http://www.colourbox.de/bild/kaffeetasse-und-loffel-auf-teller-isoliert-auf-weisem-hintergrund-bild-1632193&ei=0n7mUs3CM8Hb0QX6wIHACA&bvm=bv.59930103,d.bGE&psig=AFQjCNGtDk_dF0ZSTXAiJr1NQHGPJlOT3g&ust=1390923666906700



http://www.google.com/url?sa=i&rct=j&q=&esrc=s&frm=1&source=images&cd=&cad=rja&uact=8&docid=4opgO7wl_UfC0M&tbnid=vi_zdhAv0ViNLM:&ved=0CAUQjRw&url=http://www.juraworld.com/home_jura_world_of_coffee/news_jwoc/news_archiv_jwoc.htm?pageFilter%3D6%26reference%3D64207%26checkSum%3DD8D95B0187CD52735BE8DFBC8D45C4A7&ei=4MZwU8OuHMavOdmFgLgG&bvm=bv.66330100,d.bGE&psig=AFQjCNHzPyVA_4ohGfBcPFiV4zTtG_oiMA&ust=1399986241783132

http://www.google.com/url?sa=i&rct=j&q=&esrc=s&frm=1&source=images&cd=&cad=rja&uact=8&docid=ZXutTg8K3nAYTM&tbnid=aR5xjlweC75OMM:&ved=0CAUQjRw&url=http://eva.vn/chuyen-tinh-yeu/capuchino-cua-toi-c4a13150.html&ei=XulwU_aUNofLOIX9gPgK&bvm=bv.66330100,d.bGE&psig=AFQjCNEYir9cSPFDsnSSFQtJJd2hF5StIQ&ust=1399986305104986

Internal


ecovio® as complete packaging solution

June 29, 202114

Internal

0

20

40

60

80

100

120

140

160

180

0

500

1000

1500

2000

2500

PP Borpact ecovio® IA1652

Ch

arp

y [

kJ/m

²]H

DT

/B [

°C]

Yo

un

g's

mo

du

lus [

MP

a]

Young's modulus [MPa]

Charpy [kJ/m²]

Heat deflectiontemperatur HDT/B [°C]


Comparison of mechanical properties of Polypropylene (PP) and ecovio®

June 29, 202115

➔ ecovio® comparable to

stiff PP

Internal

Packaging – paper coating

Combination of paper and biodegradable and biobased polymers

June 29, 202116

▪ Paper has been the major packaging material

50 years ago

▪ Due to missing performance characteristics and

barrier properties (e.g. fat resistance) paper has been

largely replaced by polymers (e.g. PE)

▪ Paper has an excellent image as packaging material

(renewable and biodegradable)

▪ Using biodegradable/biobased polymers, the missing

performance and barrier properties of paper can be

compensated

Combination of paper with biodegradable and biobased polymers is leading to a

sustainable packaging solution

Internal


BASF provides biodegradable and biobased polymer solutions for bags, packaging

and agro applications

June 29, 202117

ecovio® F Mulch

ecovio® F Filmecovio® Flexible packaging

ecovio® FS Paper

ecovio® Rigid packaging

Film Applications

Packaging

Solutions

ecovio® EA Foam

Packaging

ecovio® F Film

Internal

Biodegradability understanding

What is biodegradability?

18

Biodegradation = microorganisms metabolize the polymeric material

completely to CO2, energy, water & biomass (aerobic process)

Microorganism

Cell

material

(biomass)

Energy,

CO2, Water

„Food“ biopolymers

(e.g. starch, proteins, synth. biodegr. polymers)

Humans

Food biopolymers

(e.g. starch, proteins)

Cell

material

(biomass)

Energy,

CO2, Water

Internal

Different environments

Fundamental understanding of biodegradability in all end of life options to enable

appropriate standard development and application specific product development

Elucidating structure- biodegradability relationship

cultivation

Polymer characteristics

Microorganisms and enzymes

Abiotic factors

microbial

profiling

enzyme

characterization

Fundamental understanding

19

Product development

Pe

rfo

rma

nce

Biodegradability

Assessing product performance in field trials

Field evaluation

Fundamental understanding of biodegradability

Internal

20

ecovio® is the trade

name for BASF’s

compounds based

on ecoflex® +

Polylactic acid (PLA)

Biodegradation in soil

Biodegradable mulch film ecovio® M2351 mulch


Internal

21

0

10

20

30

40

50

60

70

80

90

100

0 50 100 150 200 250 300

Bio

de

gra

da

tio

n / %

Time / days

Biodegradation of ecovio® M2351 mulch film relative to cellulose control


ecovio® M2351 mulch – Biodegradation in soil according to ISO 17556

90

At 181 days 89,1 % biodegradation

relative to Cellulose was measured

(absolute biodegradation of 94.4%

(±1.7%) –

Where is the rest?


Internal

22

microbial

biomass

1. Microbial colonization

5. Soil attachment

2. Enzymatic hydrolysis 3. Microbial metabolism

4. Microbial characterization

Sorp

tion

Desorp

tion


Decisive methods for understanding biodegradation in soil of ecovio®

mulch film

Where does the

polymer carbon

end up?


Internal

23

Where does the

polymer carbon

end up?microbial

biomass

1. Microbial colonization

5. Soil attachment

2. Enzymatic hydrolysis 3. Microbial metabolism

4. Microbial characterization

Sorp

tion

Desorp

tion



mulch film


Internal

24

◼ Cavity Ring Down Spectroscopy (CRDS) method

is sensitive to 12C- & 13C-carbon dioxide

◼ Mineralization of stable isotope labeled polymers

can be followed very accurately & position-

specifically hydrolysis &

mineralization

*13CO2

12CO2

+**

*

Picarro CRDS

calib. gases incubator valve system



mulch film


Internal

Zumstein et al.,Science

Advances 2018;4:eaas9024

25

negative control

Primary ion

beam (Cs+)

Secondary

ions

Mass

spectrometer

(12C14N; 12C13C)

poly(butylene adipate-co-terephthalate)

PBAT: labeled in adipate

Nanoscale secondary

ion mass spectrometry

(NanoSIMS)

Secondary

ele

ctr

ons

12C

14N

-io

ns

**

10 µm

13C / (12C + 13C) (%)

13C atom percent


Conversion into microbial biomass


Internal

26

For the first time

fate of polymer

from biodegradable

mulch film can be

followed



mulch film are established

microbial

biomass

5. Soil attachment

2. Enzymatic hydrolysis

Sorp

tion

Desorp

tion

Cavity ring down

spectroscopy

(CRDS)

Respirometric

measurements (O2

demand, CO2

evolution)

Nanoscale

Secondary Ion Mass

Spectrometry

(NanoSIMS)

Microorganisms & enzymes

Soil extraction and

(trace) analytics


Internal

27

Approach designed to simulate all zones in which plastic

litter is found, but deep sea is excluded

2: Surface, 0 m

3: Pelagic, 20 m4: Benthic, 40 m

1. Eulittoral ˗ intertidal with

changing water level and

occasional exposure to air

2. Pelagic (surface) ˗ free-

floating on water surface with

exposure to waves, air

and radiation

3. Pelagic (floating) ˗ free-

floating in deeper seawater

4. Bentic ˗ lying on the seafloor

in contact with sediment and

water

1: Eulittoral – tidal/beach zone

Biodegradation in marine environment

Schematic view of typical coastal situations in which plastic debris is most

commonly found


Internal

28

Biodegradation in marine environment

Exemplary results show degradation speed depends on marine zone

Eulittoral

(beach)

after 20

months

no signs of

degradationSurface

after 17,5

months (no

sample left

after 20

month)

ecovio® Sample 1 ecovio® Sample 2 LDPE

heavy

disintegration

Pelagic (20 m)

after 15

months

Benthic (sea

floor, 40 m)

after 15

months

◼ Heavy biofouling

observed for surface

and pelagic samples

◼ After 10 months: visible

signs of degradation for

ecovio® samples placed

at water surface and

beach, as well as on

sediment at 40 m

◼ LDPE film shows no

signs of degradation

beginning

disintegration


Internal

Conclusion

Fundamental understanding in a holistic approach

Elucidating structure- biodegradability relationship

cultivation

Polymer characteristics

Microorganisms and enzymes

Abiotic factors

microbial

profiling

enzyme

characterization

Fundamental understanding

29

BASF provides basic

understanding for

appropriate standard

development and

development of new

biodegradable materials

in all end of life options

Field evaluation


Internal

Use in City

Organic waste management

Food production

Biodegradation

The circular economy vision with use of biodegradable and biobased materials –

how to close the nutrient loops

PackagingMulch Films Bags

➔ Biodegradable polymers as enabler for

organic waste recycling and closing the loop

– case study e.g. Milan (Italy)


Internal


ecoflex ® and ecovio® of BASF: continuous technology and market development

31

1993: start R&D

1998: market introduction ecoflex®

2006: market introduction ecovio®

Since 2007: continuous development of ecoflex® and ecovio®

portfolio with new applications and increased biobased content

2010: startup of the new single-purpose capacity extension in

Ludwigshafen (Germany). Total capacity: 14 kta → 74 kta

Since 2011: Fundamental research for understanding of

biodegradability

Continuous R&D to improve existing products, develop new applications and enlarge

biodegradability understanding

Internal

32

“Everybody needs to have

the courage of conviction.”

Alexander von Humbold

Conclusion

The ongoing task for biopolymers …

Internal

“biodegradable and biobased

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