Development of Biobased/Biodegradable/ Compostable ... · Biobased/Biodegradable/ Compostable...

Erhan Pişkin1, Yeşim Ekinci2, Hülya Yavuz Ersan1, Sinan Eğri1,3,

Gökhan Tezcan1, Koroush Salami1, Özlem Eğri1,4, Zakir Rzaev4,

Sevda İsmailova1, Farzaneh Moghtader4

Hacettepe University

Supported by Turkish Ministry of Science, Technology and Industry

Development of Biobased/Biodegradable/

Compostable Nanocomposite Mulching Films and Active Packaging

PLASTICE October 24-25, 2011, Bologna, Italy

FOSSIL FUELS

0.2 Gtons (3%)

Polymeric Materials

7.3 Gtons

6.5 Gtons (93%)

Energy Production 0.3 Gtons (4%)

Raw Chemicals

Crude Oil

44%

Natural Gas

25%

Coal 31%

Annual Consumption

It is a pity … Fossil Fuels will finish soon … When ??

We need new resources

for energy and POLYMERS

1

10

100

1000

10000

100000

1000000

1 10 100

Price (US Dollars/kg)

Po

lym

er

Pro

du

cti

on

(to

ne

s/y

ea

r)

PP

Epoksiler

PVC LDPE ABS PET PMMA Poliasetaller

Poliamidler PC Silikonlar PPS PES PEEK

POLYMERS: Production-Price

PRODUCTION > 200 Million tones

CONSUMPTION Developed Countries > 100 kg/person/year

Developing Countries > 1-10 kg/person/year

POLYMER - WASTE

ENVIRONMENTAL CONCERNS are increasing

We need effective “waste manegement” strategies

TURKEY

Area: 777 971 km2

Population: > 70 Million

2025 .... > 95 Million 25% leaves in three big cities 60% leaves in cities

Solid waste: 450-750 g/day/person

20 Million tones/year

0

5

10

15

20

25

30

35

40

45

World

Turkey

POLYMERS IN USE

Expected life (year)

Packaging/Mulching <1 Construction 25

Electronic 15

Paints/Coatings 4

Car industry 11

Furniture 10

Industrial machinery 15

POLYMERS IN USE EXPECTED LIFES

Recyclables 13%

Destroyed 24%

Organic

Substances

63%

PLASTICS 21%

Metals 9%

Paper 47%

Glass17%

Others 6%

TURKEY

SOLID WASTE COMPOSITION

WASTE MANAGEMENT STRATEGIES

1. RECYCLING Mechanical Chemical Biological (Composting)

. It is widely used if not mixed with organic waste

. Note that properties of the polymer changes in each processing step

WASTE MANAGEMENT STRATEGIES

COMPOSTING

Microorganisms Oxygen Humidity

Organic/Compostable Materials (Carbon source)

Heat Biodegradation

CO2 + H2O

N, P, K, ...

COMPOST

Reduces significantly chemical fertilizer use; plant diseases; water consumption; erosion, etc.

Increases soil quality; production yield and product quality

Technologies are exist.

Investment cost may be a problem. Preselection is needed. Depends on the waste composition

WASTE MANAGEMENT STRATEGIES

2. INCINERATION 30300 KJ/Kg High investment cost ?

Preselection ? Air polution ? Political concerns ?

WASTE MANAGEMENT STRATEGIES

3. LAND FILLING

Damping (easy but not good)

Samitary Fields (good but expensive)

MULCHING FILMS

MULCH FILM CYCLE

Why we need to use mulching films?

1. Positive heat effects (earlier planting dates

or planting at hot weather)

2. Soil moisture retention (less water)

3. Weed management

4. Reduced fertilizer leakage/use (drip irrigation)

5. Reduced soil compaction and therefore reduced root damage

6. Reduced negatif effects of weather conditions.

MULCHING FILMS

Much Higher Quality & Yield

What we use ? Consumption ? Problems ?

1. Low density polyethylene (LDPE)

2. Use: About 1 million ton/year (worldwide) which results a huge plastics waste

3. Can be used only twice. Recyling is very difficult. They should be collected and disposed (which makes the process expensive)

MULCHING FILMS

Alternative solutions?

Use .......... “Biobased Resources”-

They are ........... ”Renewable”

and “Biodegradable”

MULCHING FILMS

BIOBASED POLYMERS

However they may be more expensive and exhibit lower

mechanical properties comparing to their alternative comodity but-non degradable thermoplastics in many applications including and agro-use

BIOBASED POLYMERS

1. Natural polymers

2. Polymers produced from biobased monomers

FROM BIO-DERIVED MONOMERS

Poly(-hydroxy acids)

e.g. Poly(lactic acid) (PLA)

BIOBASED POLYMERS

LACTIC ACID

The L (+) form is the natural one, and is naturally present in animal and human tissues as well as in numerous food products (meat, milk products, pickles, beer, etc.).

Lactic acid (called also “milk acid”) is a natural product.

Today more than half of the total consumption is produced by fermentation in which several carbohydrate sources such as whey, barley, sugarcane, soybean, milk, corn, sulfite waste liquor and potatoes can be used as substrate. Careful selection of the fermentation bacteria. Industrially used specie is Lactobacillus Delbrueckii with glucose or sucrose as substrate.

With different molecular weights (chain lengths)

with different chain compositions (copolymers)

Therefore with different mechanical properties,

and degradation rates

Poly(glycolide) (R:H)

Poly(L-lactide)

Poly(D-lactide)

Poly(D,L-lactide) a mixture of L-and D-

Poly(glycolide/lactide)

Poly(-hydroxy acids)

O H

R

- O - C - C

n Cargill-NatureWorks LLC, USA

PURAC, The Netherlands

Poly(-hydroxy acids)

Poly(-hydroxy acids)

Poly(-hydroxy acids)

OUR RELATED PRODUCTS

Poly(-hydroxy acids)

MONTHS

______________________________________________

PLLA 18-24

PDLLA 12-16

PGA 2-4

PDLLA/GA-50/50 2

PDLLA/GA-85/75 5

PDLLA/CL-90/10 2

______________________________________________

Approximate degradation time

NATURAL POLYMERS

ANIMAL VEGETAL

Proteins Cellulosics / Lignin

Fats & oils Starches

Polysaccharides Proteins / Fats & oils

Polynucleotides Polynucleotides

MICROBIAL

Polyesters

Polysaccharides

Polyphosphates

Polysulfides

PLANT

MICROBIAL

ANIMAL

PLANT-BASED

3.7 Gtons (62%)

Food-use

6 Gtons

0.3 Gtons (5%)

Non-Food Use 2 Gtons (33%)

Energy & Housing

2 kg/day/person

Annual Consumption

EAT or USE

?

PLANT BASED POLYMERS

POLYSACCARIDES

(a) Starches: wheat; potatoes; maize, etc.

(b) Cellulose : wood, straws, etc.

(c) Others: pectins; chitin/chitosan; gums, etc.

Starch

Polimer Faz Sentez ve Karakterizasyonu

Nişasta

Laktik Asit

Katalizör

Oligo - PLA PLA

Nişasta çözücü

M.Nişasta

Nişastanın Oksitlenme İle Modifikasyonu

Nişasta tekrarlayan birimi Dialdehid nişasta birimi

NANOCOMPOSITES

Barrier improvement primary advantage Platelets are typically about 1 nm thick,

typically 100-2000 nm in length & width

Also .. Increase stiffness, strength Act as nucleating agent in foams Smaller cell size, higher cell density

Act as flame retardants

Based on various types of clay, most common:

montmorillonite, hektorit, saponit, fluoromika, fluorohektorit, vermikulit, kaolinit, magadiit, etc.

CLAY NANOCOMPOSITES

Blending

and

Anneling

Organophilic

Clay

Termoplastic

Polymer “Intercalation”

NH3+

NH3+ NH3

+

NH3+

NH3+ NH3

+

Melt Intercalation

CLAY NANOCOMPOSITES

Intercalating Agents

CLAY NANOCOMPOSITES

MORE ………….

……. Active and Intelligent Packaging

Biobased/biodegradable/antibacterial/ nanocomposite polylactic acid-

thermoplastic starch based flexible food (meat) packaging films carrying intelligent

tags read out by SERS sensors

Unfilled

Filled

Clay content

CLAY NANOCOMPOSITES

THANKS ………….

……. piskin@hacettepe.edu.tr

…… erhanpiskin@biyomedtek.com