polymers from renewable resources: state of the art and

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Mariastella Scandola Dipartimento di Chimica ‘G. Ciamician’, Università di Bologna Polymers from renewable resources: state of the art and perspectives. Part 1

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Page 1: Polymers from renewable resources: state of the art and

Mariastella ScandolaDipartimento di Chimica ‘G. Ciamician’, Università di Bologna

Polymers from renewable resources: state of the art and perspectives. Part 1

Page 2: Polymers from renewable resources: state of the art and

"development that meets the needs of the present without compromising the ability of future generations to meet their own needs”

Sustainable development:

World Commission on Environment and Development’s(the Brundtland Commission) report Our Common Future (1987)

problems associated with the intensive use of oil

global warming (greenhouse gas, ozone depletion)

fossil resources depletion

Use of renewable resourcesM. Scandola - Alma Mater Università di Bologna

Page 3: Polymers from renewable resources: state of the art and

(2006)

L.Shen, J.Haufe,M.K.Patel “Product overview and market projection of emerging bio-based plastics”, PRO-BIP, final report (June 2009)

M. Scandola - Alma Mater Università di Bologna

Page 4: Polymers from renewable resources: state of the art and

Scientific publications Patents

Bio-based polymers(from Web of Science)

M. Scandola - Alma Mater Università di Bologna

Page 5: Polymers from renewable resources: state of the art and

Production of Bio-based polymers

Directly from agro-resources by extraction/separation

through biotechnology(fermentation)

POLYMER

Organic synthesis

Ex: polyamides, poleysters, PE, PET

monomers(building blocks)

Ex: cellulose, starch, natural ruber

POLYMER

Ex: bacterial polyesters

POLYMER

M. Scandola - Alma Mater Università di Bologna

Page 6: Polymers from renewable resources: state of the art and

Quantification of Bio-based Carbon

ASTM D6866: Standard Test Methods for Determining the Biobased

Content of Solid, Liquid, and Gaseous Samples Using Radiocarbon Analysis

M. Scandola - Alma Mater Università di Bologna

Page 7: Polymers from renewable resources: state of the art and

Production of Bio-based polymers

Directly from agro-resources by extraction/separation

through biotechnology(fermentation)

POLYMER

Organic synthesis

Ex: polyamides, poleysters, PE, PET

monomers(building blocks)

Ex: cellulose, starch, natural ruber

POLYMER

Ex: bacterial polyesters

POLYMER

M. Scandola - Alma Mater Università di Bologna

Page 8: Polymers from renewable resources: state of the art and

Historically, industrially exploited biopolymers 

cellulosics natural rubber

M. Scandola - Alma Mater Università di Bologna

Page 9: Polymers from renewable resources: state of the art and

Production of Bio-based polymers

Directly from agro-resources by extraction/separation

through biotechnology(fermentation)

POLYMER

Organic synthesis

Ex: polyamides, poleysters, PE, PET

monomers(building blocks)

Ex: cellulose, starch, natural ruber

POLYMER

Ex: bacterial polyesters

POLYMER

M. Scandola - Alma Mater Università di Bologna

Page 10: Polymers from renewable resources: state of the art and

60-year-old polymer

Polyamide 11 (nylon11)

11-aminoundecanoic acid

Ricinus communisOil

PA11

Polyamide 11:• resists swelling when exposed to water• highly resistant to hydrocarbons

is used to make:

• gas distribution pipes• natural gas pipelines• pressure barriers for offshore oil pipelines• fuel tanks and air brake hoses.

M. Scandola - Alma Mater Università di Bologna

Page 11: Polymers from renewable resources: state of the art and

Production of Bio-based polymers

Directly from agro-resources by extraction/separation

through biotechnology(fermentation)

POLYMER

Organic synthesis

Ex: polyamides, poleysters, PE, PET

monomers(building blocks)

Ex: cellulose, starch, natural ruber

POLYMER

Ex: bacterial polyesters

POLYMER

M. Scandola - Alma Mater Università di Bologna

Page 12: Polymers from renewable resources: state of the art and

Bacterial polyesters

Polyhydroxyalkanoates (PHAs)

intracellular granules

(biosynthesized as C and energy source)

Polyhydroxybutyrate (PHB) homopolymer

(highly crystalline)

(Tg = 0°C, Tm = 175°C)

-(O-CH-CH2-CO)n-CH3

M. Scandola - Alma Mater Università di Bologna

Page 13: Polymers from renewable resources: state of the art and

properties greatly changewith unit type and composition

High modulus rigid materials rubbers

-(O-CH-CH2-CO)n-

R

where R = (CH2)m-CH3 with m = 0…8

some microorganisms are very versatile bioreactors for the synthesis of PHA copolymers

PHAs

> 100 different monomers incorporated in PHAs (research!) Steinbuchel, A.; Valentin, H. E. FEMS Microbiol. Lett. 1995, 128, 219-228

M. Scandola - Alma Mater Università di Bologna

Page 14: Polymers from renewable resources: state of the art and

Production of Bio-based polymers

Directly from agro-resources by extraction/separation

through biotechnology(fermentation)

POLYMER

Organic synthesis

Ex: polyamides, poleysters, PE, PET

monomers(building blocks)

Ex: cellulose, starch, natural ruber

POLYMER

Ex: bacterial polyesters

POLYMER

M. Scandola - Alma Mater Università di Bologna

Page 15: Polymers from renewable resources: state of the art and

(100% % ‘bio-based’)

Monomer from biomass fermentation

+

(x % ‘bio-based’)

M. Scandola - Alma Mater Università di Bologna

Page 16: Polymers from renewable resources: state of the art and

PLA

2 configurations: D, L

(from fermentation: L monomer)

P(L)LA (homopolymer)chain regularity

can crystallizeTg = 60°CTm = 175°C

P(D,L)LA (copolymer)chain irregularity

crystallization inhibited

M. Scandola - Alma Mater Università di Bologna

Page 17: Polymers from renewable resources: state of the art and

Tmelting

amount of crystal phase Tmelting

function of D-unit

content

D.W. Grijpma, A.J. Pennings, Makromol Chem. Phys. 1994

a large polymer family

PLA

M. Scandola - Alma Mater Università di Bologna

Page 18: Polymers from renewable resources: state of the art and

P(L)LA P(D)LA

Tm = 170°C

+

Tm = 230°C

M. Scandola - Alma Mater Università di Bologna

Page 19: Polymers from renewable resources: state of the art and

GLOBAL POLYLACTIC ACID (PLA) MARKET SHARE FOR 2012 –% BREAKDOWN BY END-USER

Market Research Reporthttp://www.researchandmarkets.com/research/42glsg/polylactic_acidPolylactic Acid (PLA) - A Global Market Watch, 2011 - 2016

M. Scandola - Alma Mater Università di Bologna

Page 20: Polymers from renewable resources: state of the art and

historically

alternative

FEEDSTOCK

Strong debate: food conflict??

alternative feedstocks

Page 21: Polymers from renewable resources: state of the art and

Bio-ethylene

fertilizer

combustion to produce heat

M. Scandola - Alma Mater Università di Bologna

Page 22: Polymers from renewable resources: state of the art and

Green polyethylene plant (200kt/year)

“each ton of green polyethylene removes 2.5 tons of CO2 from the atmosphere”

(September 2010, Brazil, Rio Grande do Sul)

Green-PE

Up to 400kt/year in 2015

JV

Announced production:350kt/year in 2015 (Brazil)

Many large companies interested in the bioethylene businessM. Scandola - Alma Mater Università di Bologna

Page 23: Polymers from renewable resources: state of the art and

Paulien F. H. Harmsen et al.Biofuels, Bioprod. Bioref. 8:306–324 (2014)

R&D

Page 24: Polymers from renewable resources: state of the art and

R&D

Page 25: Polymers from renewable resources: state of the art and

Bio-3HP (3-hydroxypropionic acid)

Bio-acrylic acid

+

+

M. Scandola - Alma Mater Università di Bologna

Page 26: Polymers from renewable resources: state of the art and

Bio-based monomers for rubbers

Genetically modifiedmicroorganisms grow on glucose, sucrose, glycerolor plant oils to produce

(MacGregor Campbell, New Scientist, 29 March 2010)

Bio-isoprene

M. Scandola - Alma Mater Università di Bologna

Page 27: Polymers from renewable resources: state of the art and

Routes to bio-based rubbers

Page 28: Polymers from renewable resources: state of the art and

Goodyear and Genencor (part of DuPont )

Michelin and Amyris bio-isopreneBridgestone Corp. and Ajinomoto Co., Inc.

Eni/Versalis and Genomatica bio-butadiene

Lanxess and GEVO bio isobutylene

Bio-based rubbers

M. Scandola - Alma Mater Università di Bologna

Page 29: Polymers from renewable resources: state of the art and

(100% % ‘bio-based’)

Monomer from biomass fermentation

+

(x % ‘bio-based’)

M. Scandola - Alma Mater Università di Bologna

Page 30: Polymers from renewable resources: state of the art and

bio-based di-amine/di-acid for Nylons

1,5 pentamethylenediamine monomer

Sebacic acid (C10)

M. Scandola - Alma Mater Università di Bologna

Page 31: Polymers from renewable resources: state of the art and

Bio-based Polyamides

Page 32: Polymers from renewable resources: state of the art and

Bio-PDO (1,3-propandiol)

Products: SusterraTM , ZemeaTM

Bio-PDO (1,3-propandiol)

by genetic engineering

a single bacterium (E.coli)

in nature: 2 microorganisms

M. Scandola - Alma Mater Università di Bologna

Page 33: Polymers from renewable resources: state of the art and

3GT (Sorona®) DuPont

OC

CC

O

OC

OC

OC

CC

O

OC

OO

CC

CO

OC

OC

OC

CC

O

OC

OHO

CC

COHHO

CC

COH C

O

OHC

HO

OC

O

OHC

HO

O++1,3-Propanediol

(3G)1,3-Propanediol

(3G)Polypropylene terephthalate

(3GT)Polypropylene terephthalate

(3GT)Terephthalatic AcidTerephthalatic Acid

PET OR 2GT (polyester)

OC

CO

CO

CO

CC

OO

CCO

O

OC

CO

CO

CO

CC

OO

CCO

O

CO

OHC

HO

OC

O

OHC

HO

O

HOC

COH

HOC

COH +

Terephthalatic AcidTerephthalatic Acid Polyethylene terephthalate(PET, 2GT)

Polyethylene terephthalate(PET, 2GT)

Polymers from Bio-PDO

Sorona fibres Sorona EP engineering plastics applications(electric, electronic connectors, housings)

M. Scandola - Alma Mater Università di Bologna

Page 34: Polymers from renewable resources: state of the art and

Bio-succinic acid

Glucose

Recombinant E.coli in anaerobic conditionsEnzymatic process

succinic acid plant (France, 3000 ton/year) (350,000 liter commercial-scale fermenter)

joint venture to build a bio-succinic plantin Ontario 30kton/year (2014) BioAmber and Mitsui & Co

M. Scandola - Alma Mater Università di Bologna

Page 35: Polymers from renewable resources: state of the art and

http://www.icis.com/blogs/green-chemicals/2011/11/bioamber-mitsui-jv-to-build-su/

M. Scandola - Alma Mater Università di Bologna

Page 36: Polymers from renewable resources: state of the art and

Bio-PET??? Ethylene glycol from bio-ethanol….OK

Terephtalic acid???

Bio-routes to terephthalic acid

3

O

2

3

O OH CH

 

  

2  

-H O  

CH O OH

 Paraxylene is converted into

Terephthalic Acid

«BioForming process for converting plant-based sugars and agriculturalresidues into a full range of products»

The first commercial plant - 2015 paraxylene (PX).

Production capacity - from 30kt/year to 225 kt/year

M. Scandola - Alma Mater Università di Bologna

Page 37: Polymers from renewable resources: state of the art and

Bio-routes to terephthalic acid

Converting fermentation-derived isobutanol to paraxylene

by using traditional chemical processes:

1. dehydration2. dimerization3. cyclization

Commercial production of bio-paraxylene – expexted

M. Scandola - Alma Mater Università di Bologna

Page 38: Polymers from renewable resources: state of the art and

patent - production of para-xylene from terpenes(i.e. limonene from citrus fruits)

More green routes to terephthalic acid

single-step catalytic fast pyrolysis process to convert biomass to benzene, toluene and xylene;

convertion of sugar-based muconic acid to phtalic acic

biomass gasification and "syngas-to-green" patented processing up to 80% aromatics.

http://www.icis.com/Articles/2012/03/12/l

M. Scandola - Alma Mater Università di Bologna

Page 39: Polymers from renewable resources: state of the art and

Furan dicarboxylic acid as an alternative to terephthalic acid

PEF bottle (better oxygen and carbon dioxide barrier than PET)

New sugar-based 2,5-furandicarboxylic acid (FDCA), which can be reacted with EG to make polyethylene furanoate (PEF), as an alternative to PET resin

Commercial production of FDCA and PEF - 2017

M. Scandola - Alma Mater Università di Bologna

Page 40: Polymers from renewable resources: state of the art and

http://greenchemicalsblog.com/2012/10/01/coca-cola-picks-2nd-bio-eg-supplier/

Multi-million dollar partnership agreements with Virent, Gevo and Avantium

(Plant Bottle: 2014 Sustainable Bio Awards)

M. Scandola - Alma Mater Università di Bologna

Page 41: Polymers from renewable resources: state of the art and

Bio-based polymer

Biodegradability ???

EN 13432 - plastic product compostability

ASTM D5338 - 98(2003) Standard Test Method for Determining Aerobic Biodegradation of Plastic Materials Under Controlled Composting Conditions

ASTM D6400 - 04 Standard Specification for Compostable Plastics

Etc….

M. Scandola - Alma Mater Università di Bologna

Page 42: Polymers from renewable resources: state of the art and

Biodegradable plastic: a degradable plastic in which the degradation results from the action of naturally-occurring micro-organisms such as bacteria, fungi and algae.

fragments enzyme

CO2

ASTM definition

POLYMER

FRAGMENT

(mineralization)

BIOMASS, H2O, CO2 and/or CH4

outside ofthe cell

withinthe cell

M. Scandola - Alma Mater Università di Bologna

Page 43: Polymers from renewable resources: state of the art and

L.Shen, J.Haufe,M.K.Patel “Product overview and market projectionof emerging bio-based plastics”, PRO-BIP, final report (June 2009)

M. Scandola - Alma Mater Università di Bologna

Page 44: Polymers from renewable resources: state of the art and

A very misleading definition!!!

M. Scandola - Alma Mater Università di Bologna

Page 45: Polymers from renewable resources: state of the art and

Conclusions

Page 46: Polymers from renewable resources: state of the art and

Macromol. Chem. Phys. 2013, 214, 159−174

Org. Biomol. Chem. 2014, 12, 2834-2849

Polym. Deg. Stab. 2013, 98 1898-1907

Green Chem. 2014, 16, 950-963

ACS Macro Lett. 2013, 2, 550−554

Bio-based polymers

M. Scandola - Alma Mater Università di Bologna

Page 47: Polymers from renewable resources: state of the art and

Expected remarkable growth

M. Scandola - Alma Mater Università di Bologna

Page 48: Polymers from renewable resources: state of the art and

M. Scandola - Alma Mater Università di Bologna

Page 49: Polymers from renewable resources: state of the art and

Bio-based sustainable?

M. Scandola - Alma Mater Università di Bologna

Page 50: Polymers from renewable resources: state of the art and

(lack of data after company gate!)

Life cycle assessment for bio-based polymers is DIFFICULT!

LCA data are mostly ONLY cradle-to gate

RESOURCES- Fossil- Renewable

PRODUCTION+

MANUFACTUREUSE DISPOSAL

cradle-to-gate

cradle-to-cradle

cradle-to-grave

M. Scandola - Alma Mater Università di Bologna

Page 51: Polymers from renewable resources: state of the art and

Trends (sustainability)

Synthesis of traditional polymers using bio-based building blocks (savingoil resources, ‘carbon footprint’)

Synthesis of new polymers from bio-resources with additionalfunctionalities for specific applications (health, agriculture, marine ecc.)

Optimization of bio-based polymers production processes aimedat drastic cost reduction

Selection of uncommon non-food crops to be cultivated in low-fertility abandoned land (land recovery)

Use of waste (waste valorization!)

Innovation in feedstock

Interest towards the use of gas as feedstock alternative to biomass

M. Scandola - Alma Mater Università di Bologna