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

"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

(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

Scientific publications Patents

Bio-based polymers(from Web of Science)


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


Quantification of Bio-based Carbon

ASTM D6866: Standard Test Methods for Determining the Biobased

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





POLYMER

Organic synthesis




POLYMER


POLYMER


Historically, industrially exploited biopolymers

cellulosics natural rubber





POLYMER

Organic synthesis




POLYMER


POLYMER


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.





POLYMER

Organic synthesis




POLYMER


POLYMER


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


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





POLYMER

Organic synthesis




POLYMER


POLYMER


(100% % ‘bio-based’)

Monomer from biomass fermentation

+

(x % ‘bio-based’)


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


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


P(L)LA P(D)LA

Tm = 170°C

+

Tm = 230°C


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


historically

alternative

FEEDSTOCK

Strong debate: food conflict??

alternative feedstocks

Bio-ethylene

fertilizer

combustion to produce heat


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

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

R&D

Bio-3HP (3-hydroxypropionic acid)

Bio-acrylic acid

+

+


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


Routes to bio-based rubbers

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


(100% % ‘bio-based’)

Monomer from biomass fermentation

+

(x % ‘bio-based’)


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

1,5 pentamethylenediamine monomer

Sebacic acid (C10)


Bio-based Polyamides

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


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)


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


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


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


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


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


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


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)


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….


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


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


A very misleading definition!!!


Conclusions

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


Expected remarkable growth


Bio-based sustainable?


(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


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


Polymers from renewable resources: state of the art and ...

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