Polymers from renewable resources: state of the art and perspectives. Part 1 Mariastella Scandola Dipartimento di Chimica G. Ciamician, Università di Bologna
Sustainable development: "development that meets the needs of the present without compromising the ability of future generations to meet their own needs 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 resources
(2006) L.Shen, J.Haufe,M.K.Patel Product overview and market projection of emerging bio-based plastics, PRO-BIP, final report (June 2009)
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 Ex: cellulose, starch, natural ruber Organic synthesis monomers (building blocks) POLYMER Ex: bacterial polyesters POLYMER Ex: polyamides, poleysters, PE, PET
Quantification of Bio-based Carbon ASTM D6866: Standard Test Methods for Determining the Biobased Content of Solid, Liquid, and Gaseous Samples Using Radiocarbon Analysis
Production of Bio-based polymers Directly from agro-resources by extraction/separation through biotechnology (fermentation) POLYMER Ex: cellulose, starch, natural ruber Organic synthesis monomers (building blocks) POLYMER Ex: bacterial polyesters POLYMER Ex: polyamides, poleysters, PE, PET
Historically, industrially exploited biopolymers cellulosics natural rubber
Production of Bio-based polymers Directly from agro-resources by extraction/separation through biotechnology (fermentation) POLYMER Ex: cellulose, starch, natural ruber Organic synthesis monomers (building blocks) POLYMER Ex: bacterial polyesters POLYMER Ex: polyamides, poleysters, PE, PET
60-year-old polymer Polyamide 11 (nylon11) PA11 Ricinus communis Oil 11-aminoundecanoic acid 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.
Production of Bio-based polymers Directly from agro-resources by extraction/separation through biotechnology (fermentation) POLYMER Ex: cellulose, starch, natural ruber Organic synthesis monomers (building blocks) POLYMER Ex: bacterial polyesters POLYMER Ex: polyamides, poleysters, PE, PET
Bacterial polyesters Polyhydroxyalkanoates (PHAs) intracellular granules (biosynthesized as C and energy source) Polyhydroxybutyrate (PHB) homopolymer (highly crystalline) (T g = 0 C, T m = 175 C) -(O-CH-CH 2 -CO) n - CH 3
PHAs -(O-CH-CH 2 -CO) n - R where R = (CH 2 ) m -CH 3 with m = 0 8 some microorganisms are very versatile bioreactors for the synthesis of PHA copolymers properties greatly change with unit type and composition High modulus rigid materials rubbers > 100 different monomers incorporated in PHAs (research!) Steinbuchel, A.; Valentin, H. E. FEMS Microbiol. Lett. 1995, 128, 219-228
Production of Bio-based polymers Directly from agro-resources by extraction/separation through biotechnology (fermentation) POLYMER Ex: cellulose, starch, natural ruber Organic synthesis monomers (building blocks) POLYMER Ex: bacterial polyesters POLYMER Ex: polyamides, poleysters, PE, PET
Monomer from biomass fermentation (100% % bio-based ) + (x % bio-based )
PLA 2 configurations: D, L (from fermentation: L monomer) P(L)LA (homopolymer) chain regularity can crystallize Tg = 60 C Tm = 175 C P(D,L)LA (copolymer) chain irregularity crystallization inhibited
T melting amount of crystal phase T melting function of D-unit content D.W. Grijpma, A.J. Pennings, Makromol Chem. Phys. 1994 PLA a large polymer family
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 Report http://www.researchandmarkets.com/research/42glsg/polylactic_acid Polylactic Acid (PLA) - A Global Market Watch, 2011-2016
FEEDSTOCK historically alternative Strong debate: food conflict?? alternative feedstocks
Bio-ethylene combustion to produce heat fertilizer
Green-PE Green polyethylene plant (200kt/year) (September 2010, Brazil, Rio Grande do Sul) Up to 400kt/year in 2015 each ton of green polyethylene removes 2.5 tons of CO 2 from the atmosphere JV Announced production:350kt/year in 2015 (Brazil) Many large companies interested in the bioethylene business
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 + +
Bio-based monomers for rubbers Genetically modified microorganisms grow on glucose, sucrose, glycerol or plant oils to produce Bio-isoprene (MacGregor Campbell, New Scientist, 29 March 2010)
Routes to bio-based rubbers
Bio-based rubbers Goodyear and Genencor (part of DuPont ) Michelin and Amyris bio-isoprene Bridgestone Corp. and Ajinomoto Co., Inc. Lanxess and GEVO bio isobutylene Eni/Versalis and Genomatica bio-butadiene
Monomer from biomass fermentation (100% % bio-based ) + (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) in nature: 2 microorganisms Products: Susterra TM, Zemea TM by genetic engineering a single bacterium (E.coli)
Polymers from Bio-PDO HO C OH C C 1,3-Propanediol (3G) + HO O C C O OH Terephthalatic Acid O O C O C C C C C C O C O O Polypropylene terephthalate (3GT) O O C 3GT (Sorona ) DuPont HO C C OH + HO C O O C OH Terephthalatic Acid O C C O C O PET OR 2GT (polyester) O C O C O C C O C O Polyethylene terephthalate (PET, 2GT) Sorona fibres Sorona EP engineering plastics applications (electric, electronic connectors, housings)
Bio-succinic acid Glucose Enzymatic process Recombinant E.coli in anaerobic conditions succinic acid plant (France, 3000 ton/year) (350,000 liter commercial-scale fermenter) BioAmber and Mitsui & Co joint venture to build a bio-succinic plant in Ontario 30kton/year (2014)
http://www.icis.com/blogs/green-chemicals/2011/11/bioamber-mitsui-jv-to-build-su/
Bio-PET??? Ethylene glycol from bio-ethanol.ok Bio-routes to terephthalic acid Terephtalic acid??? «BioForming process for converting plant-based sugars and agricultural residues into a full range of products» The first commercial plant - 2015 paraxylene (PX). Production capacity - from 30kt/year to 225 kt/year CH 3 O OH O 2 2 -H O CH 3 O OH Paraxylene is converted into Terephthalic Acid
Bio-routes to terephthalic acid Converting fermentation-derived isobutanol to paraxylene by using traditional chemical processes: 1. dehydration 2. dimerization 3. cyclization Commercial production of bio-paraxylene expexted
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 patent - production of para-xylene from terpenes (i.e. limonene from citrus fruits) 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 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 PEF bottle (better oxygen and carbon dioxide barrier than PET) Commercial production of FDCA and PEF - 2017
http://greenchemicalsblog.com/2012/10/01/coca-cola-picks-2nd-bio-eg-supplier/ (Plant Bottle: 2014 Sustainable Bio Awards) Multi-million dollar partnership agreements with Virent, Gevo and Avantium
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.
ASTM definition Biodegradable plastic: a degradable plastic in which the degradation results from the action of naturally-occurring micro-organisms such as bacteria, fungi and algae. POLYMER fragments CO 2 enzyme outside of the cell FRAGMENT within the cell (mineralization) BIOMASS, H 2 O, CO 2 and/or CH 4
L.Shen, J.Haufe,M.K.Patel Product overview and market projection of emerging bio-based plastics, PRO-BIP, final report (June 2009)
A very misleading definition!!!
Conclusions
Bio-based polymers Org. Biomol. Chem. 2014, 12, 2834-2849 Polym. Deg. Stab. 2013, 98 1898-1907 ACS Macro Lett. 2013, 2, 550 554 Macromol. Chem. Phys. 2013, 214, 159 174 Green Chem. 2014, 16, 950-963
Expected remarkable growth
Bio-based sustainable?
Life cycle assessment for bio-based polymers is DIFFICULT! cradle-to-gate RESOURCES - Fossil - Renewable PRODUCTION + MANUFACTURE USE DISPOSAL cradle-to-grave cradle-to-cradle LCA data are mostly ONLY cradle-to gate (lack of data after company gate!)
Trends (sustainability) Synthesis of traditional polymers using bio-based building blocks (saving oil resources, carbon footprint ) Synthesis of new polymers from bio-resources with additional functionalities for specific applications (health, agriculture, marine ecc.) Optimization of bio-based polymers production processes aimed at drastic cost reduction Innovation in feedstock Selection of uncommon non-food crops to be cultivated in lowfertility abandoned land (land recovery) Use of waste (waste valorization!) Interest towards the use of gas as feedstock alternative to biomass