polymers from renewable resources: state of the art and
TRANSCRIPT
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)
M. Scandola - Alma Mater Università di Bologna
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
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
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
Historically, industrially exploited biopolymers
cellulosics natural rubber
M. Scandola - Alma Mater Università di Bologna
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
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
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
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
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
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
(100% % ‘bio-based’)
Monomer from biomass fermentation
+
(x % ‘bio-based’)
M. Scandola - Alma Mater Università di Bologna
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
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
P(L)LA P(D)LA
Tm = 170°C
+
Tm = 230°C
M. Scandola - Alma Mater Università di Bologna
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
historically
alternative
FEEDSTOCK
Strong debate: food conflict??
alternative feedstocks
Bio-ethylene
fertilizer
combustion to produce heat
M. Scandola - Alma Mater Università di Bologna
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
R&D
Bio-3HP (3-hydroxypropionic acid)
Bio-acrylic acid
+
+
M. Scandola - Alma Mater Università di Bologna
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
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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
M. Scandola - Alma Mater Università di Bologna
(100% % ‘bio-based’)
Monomer from biomass fermentation
+
(x % ‘bio-based’)
M. Scandola - Alma Mater Università di Bologna
bio-based di-amine/di-acid for Nylons
1,5 pentamethylenediamine monomer
Sebacic acid (C10)
M. Scandola - Alma Mater Università di Bologna
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
M. Scandola - Alma Mater Università di Bologna
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
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
http://www.icis.com/blogs/green-chemicals/2011/11/bioamber-mitsui-jv-to-build-su/
M. Scandola - Alma Mater Università di Bologna
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
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
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
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
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
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
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
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
A very misleading definition!!!
M. Scandola - Alma Mater Università di Bologna
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
M. Scandola - Alma Mater Università di Bologna
Expected remarkable growth
M. Scandola - Alma Mater Università di Bologna
M. Scandola - Alma Mater Università di Bologna
Bio-based sustainable?
M. Scandola - Alma Mater Università di Bologna
(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
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