IUPAC Green Chemistry

IUPAC Green Chemistry

Singularidades da Borracha Natural e Celulose Abrem Novas Perspectivas Fernando Galembeck University of Campinas IPT – Institute for Technological Research (São Paulo) GG&FG Consultores 11/9/16 1 Synopsis • Biomass: food, energy and raw materials • in the past • present situation • scenarios • a matter of policy • Materials from biomass • Natural rubber • Cellulose • Prospects and Needs 11/9/16 2 In the past: biomass provided food, energy and raw materials Food: 100% Energy: wood Raw materials: wood, natural fibers + minerals Consequence: land change by Sir Mark Walport, Dec 2013 http://www.slideshare.net/bis_foresight/natural-history-museum-annual-science-lecture-2013 11/9/16 3 Current losses and gains 11/9/16 http://www.caithness.org/photos/nature/millenniumecosystem/14.jpg 4 Then came coal, oil and gas 11/9/16 https://notable.files.wordpress.com/2007/04/energy-per-capita.png 5 Abundant oil? Make protein from oil! • Use of hydrocarbon fractions for production of single-cell protein • Nine plants in the Soviet Union ranged from 50 to 240,000 tons/year. • http://www.nytimes.com/1973/11/10/archives/soviet-plant-to-convert-oil-to-protein-for-feed-use-of-yeast.htm • Unesco Science Prize, 1976 France “pour ses conclusions “for his findings on the Alfred Champagnat sur la production à la low-cost mass BP's Lavera Oil Refinery in France chaîne et à bas coût de production of new nouveaux proteines proteins from provenant du pétrole” petroleum” http://unesdoc.unesco.org/images/0011/001111/111158E.pdf 11/9/16 6 Concern: resource depletion. World 3 model NATURAL RESOURCES População POPULATION Produção industrial FOOD INDUSTRIAL SERVICES PRODUCTION POLLUTION 11/9/16 7 http://polynomial.me.uk/tag/science/ New policies favored renewable sources 2014: Estimated renewable energy share of global final energy consumption. Fossil fuels Modern renewables All 10.3% renewables Traditional 19.2% biomass 8.9% NuclearNuclear 2.5%2.5% (*) RENEWABLES 2016- Global Status Report. Renewable Energy Policy Network for 21st Century, p. 28. http://www.ren21.net/wp-content/uploads/2016/06/GSR_2016_Full_Report.pdf, accessed, on 12 July, 2016. 11/9/16 8 The Food Crisis (2007) • The ”Food riots” • FAO Food Price Index rose to 220 (Jul 2008) and 238(2011) • Causes: • Rising biofuel production from corn, sugarcane, palm oil • Wild commodity speculation, pre 2008 financial crisis • Climate, drought By Jashuah - Own work by uploader, data from Food and Agriculture Organization, CC BY-SA 3.0, https://11/9/16 commons.wikimedia.org/w/index.php?curid=19394247 9 Speculation on commodities • Food price increase fueled by wild commodity speculation, pre-2008 FAO Food Price Index financial crisis • Phosphate rock prices: 50 to 460 US$/tonne (Jan Jan 2007 Jan 2009 2007 to July 2008) Phosphate rock price http://www.australianminesatlas.gov.au/a imr/images/phosphate-figure3.jpg http://en.mercopress.com/data/cache/noticias/37399/0x0 /food-protesters.jpg 11/9/16 10 FAO Hunger Map, 2015 Legend Target achieved Target not achieved, slow progress Target not achieved, lack of progress or deterioration http://www.fao.org/3/a-i4674e.pdf 11/9/16 11 A matter of policy: Global Hunger Index scores 1990 1995 2000 2005 2013 Brazil 8.7 7.6 6.4 <5 <5 Angola 39.5 38.5 31.6 22.7 19.1 India 32.6 27.1 24.8 24.0 21.3 China 13.0 10.4 8.4 6.7 5.5 Vietnam 30.9 25.1 18.1 13.7 7.7 ≥ 30.0 extremely Compound index based on: alarming (1) the percentage of people who are under- nourished, (2) 20.0–29.9 alarming the percentage of children younger than age five who are 10.0–19.9 serious underweight, and (3) the mortality rate 5.0–9.9 moderate of children younger than age five < 5.0 – low http://dx.doi.org/10.7910/DVN/22795 11/9/16 12 Products from sugarcane • Sugarcane was introduced in South and Central America in the 16th century, to produce sugar. • Sugar crystallization residues were fermented to produce ethanol. • In 1976: 2nd oil crisis led the government to create subsidies for fuel ethanol production. • In 1990: subsidies were eliminated in 90% of the producing areas. • Today: sugarcane is the biomass input for making ethanol, butanol, polyethylene, wax, green solvents and surfactants, nanosilica, cellulose, paper and pulp, microcrystalline cellulose, PHB-and other thermoplastics, lysine (>600,000 tons/year), electricity. 11/9/16 13 New products Amyris Inc. (US): Myralene™-10 – New high-performance, sustainably sourced and cost-competitive solvent made from β-farnesene New high-performance, cost-competitive solvent made from β-farnesene Produced in Brazil on a commercial scale by fermentation of sugarcane juice using special strains of baker's yeast. SIP Ltd (UK): SIPDRILL RS – First renewable, hydrocarbon drilling base fluid for high performance drilling mud systems. Renewable alkene designed for use in high performance drilling mud systems. SIPDRILL RS is 100% hydrocarbon, manufactured via the proprietary fermentation of sustainable sugar, producing farnesane, ß-farnesene and n-hexadecene. • www.biowerkstoff-kongress.de 11/9/16 14 Biofuels contribute to food security “…biofuels may offer an opportunity to improve food security. Yet, for many poorer countries in Africa and elsewhere, biofuels may be better viewed as a potential export or as a means for reducing fossil fuel imports. …producing conventional biofuels in low-income countries could raise rural incomes beyond what is required to offset rising food prices. Studies in Ethiopia: … farmers’ participation in biofuel programs encouraged greater use of fertilizers and improved farming technologies, leading to higher food-crop productivity and better food security during the year. One precondition for success, however, was farmers’ access to high-quality, productive biofuel crops.” C. Arndt, S. Msangi and J. Thurlow, Fueling the path to food security, IFPRI Global Food Policy 11/9/16 Report 2016 p.63 15 Unique properties of materials derived from biomass • Natural Rubber, Cellulose • Electrostatic Adhesion • Natural Rubber accounts for 42% of global elastomer consumption • Essential to tire and anti-vibration industries Rubber Statistical Bulletin April-June edition, quoted by S. Rolere, C. Cazevielle, J. Saint-Beuve and F. Bonfils in European Polymer Journal (2016) 11/9/16 16 The “mistery of natural rubber” • Synthetic rubber does not show the same properties as natural rubber • ”In general, as the tire size increases and the level of punishment the tire will take goes up, the amount of natural rubber increases due to natural rubber's good shear resistance, load bearing capability, and high level of resistance to cuts.” Josh Velson in https://www.quora.com/Is-natural-rubber-a-substitute-for-synthetic-rubber-in-tire-manufacturing • Which is the role of the non-rubber constituents (inorganics, proteins and phospholipids NR properties? • Yasuyuki Tanaka - Structural Characterization of Natural Polyisoprenes-Solve the Mystery of Natural Rubber Based on Structural Study, RC&T 74 (3) 355 (2001) 11/9/16 17 Adherent mineral nanoparticles in natural rubber • ESI-TEM thin film elemental maps of dialyzed natural rubber latex film • C, N densification BF 200 nm C around the S inorganic particles: adhesion • Rippel, M.M. et al. Analytical Chemistry, 2002 N P Al 11/9/16 18 Preparation of nanocomposites in aqueous media using latex Varghese, S., Karger-Kocsis, J., Polymer, 2003, 44, 4921. Wu, Y.P., Wang, Y.Q., Zhang H.F. et al. J. Compos. Sci. Tech. 2005, 65, 1195 Valadares, L. F., Leite, C. A. P., Galembeck, F., Polymer, 2006, 47, 672. Valadares, L. F., Murakami, M. M., Rippel, M. M., Galembeck, F., PI0301193-3, INPI, 2003. 11/9/16 19 Rubber-clay nanocomposite mechanical properties 10 20 phr 9 30 phr E = 109 MPa • Tensile testing: 8 E = 223 MPa 7 Modulus 6 10 phr increases to 250 E = 31 MPa 5 times 5 phr Stress [MPa] Stress 4 E = 6.5 MPa 3 Maximum stress 2 increases up to 1 Natural rubber 3.5 times E = 0.9 MPa 0 0 100 200 300 400 500 600 700 800 900 1000 1100 1200 Strain [%] Valadares, L. F., Leite, C. A. P., Galembeck, F., Polymer, 2006, 47, 672. 11/9/16 20 Clay within rubber: strong polymer – clay adhesion Valadares, L. F., Leite, C. A. P., Galembeck, F., Polymer, 2006, 47, 672. 11/9/16 21 Lower xylene swelling 5Natural rubber 10 phr clay 2500 30 phr clay 4 2000 x/x y/y x/x z/z 3 1500 y/y 30 phr Natural z/z y 2 rubber Mass uptake Mass [%] 1000 z x 1cm 1 500 (phr = per hundred rubber) 0 0 0 20 40 60 80 100 120 0 20 40 60 80 100 120 Time [min] Time [min] 11/9/16 22 Composite formation and stability • Capillary adhesion during drying • Electrostatic adhesion in the dry monolith • Both are controlled by interfacial properties • Water-based processes for making composites from incompatible materials Valadares, L.F; Bragança, F.D.; Linares, E.; Galembeck, F. J. Phys Chem C 112 (2008) 8534-8544. 11/9/16 23 Water is a general- purpose cohesive agent A styrene-acrylic resin cast The same but with clay: on polyethylene: poor film, good film, good adhesion poor adhesion to PE 11/9/16 24 Morphology – SEM SEI SEI Starch/rubber/clay Starch/rubber BEI •Good compatibility between rubber and starch. •Clay modifies starch/rubber blend morphology. 11/9/16 25 Electrostatic contributions • Latex blends and nanocomposites display complex charge patterns. • Charge patterns are modified due to ion transfer. • Charge distribution contributes to increased compatibility between phases. • Compatibility independent on bulk phase properties. • Unique combinations of mechanical properties are obtained. • Nanoparticles produce more pronounced effects. 11/9/16 26 Alkaline cellulose solutions • Cellulose is amphiphilic and this is the reason for its insolubility.

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