NATURAL POLYMERS MU SCI 4_2 2018 1 NATURAL POLYMERS 4 Lignin, Humic acids etc. Dr. Ladislav Pospíšil 29716@mail.muni.cz January 2018/4_2 Time schedule January 2018/4_2 NATURAL POLYMERS MU SCI 4_2 2018 2 LECTURE SUBJECT 1 Introduction to the subject – Structure & Terminology of nature polymers, literature 2 Derivatives of acids – natural resins, drying oils, shellac 3 Waxes 4 Plant (vegetable) gums, Polyterpene – natural rubber (extracting, processing and modification), Taraxacum_kok-saghyz 5 Polyphenol – lignin, humic acids 6 Polysaccharides I – starch 7 Polysaccharides II – celullosis 8 Protein fibres I 9 Protein fibres II 10 Casein, whey, protein of eggs 11 Identification of natural polymers Laboratory methods of natural polymers’ evaluation Tree – Approximate Composition January 2018/4_2 NATURAL POLYMERS MU SCI 4_2 2018 3 PART approx. % w/w Tree stump + plant root system 20 Branches 15 Tree trunk – divided below 65 Treetop 5 Bark 5 The only approx. 55 % w/w of the Tree BIOMASS is so converted to the Sawtimber or the Wood pulp! January 2018/4_2 NATURAL POLYMERS MU SCI 4_2 2018 4 COMPOSITION of the WOOD (ELEMENTS) Component Content approx. ( % w/w) Carbon 50 Oxygen 42 Hydrogen 6 Nitrogen 1 Other elements 1 COMPOSITION of the WOOD (Polymers & Oligomers) Component Content approx. ( % w/w) Cellulose 40 – 50 Lignin 20 – 30 Hemicellulose 20 – 30 Water Up to 14 Other (e.g. Terpenes, Waxes, Rosins, Fatty acids, Resin acids, Pectines etc.) The Rest to 100 WOOD – Approximate Composition January 2018/4_2 NATURAL POLYMERS MU SCI 4_2 2018 5 •The chemical composition of wood varies from species to species, but is approximately 50% carbon, 42% oxygen, 6% hydrogen, 1% nitrogen, and 1% other elements (mainly calcium, potassium, sodium, magnesium, iron, and manganese) by weight.[21] Wood also contains sulfur, chlorine, silicon, phosphorus, and other elements in small quantity. •Aside from water, wood has three main components. Cellulose, a crystalline polymer derived from glucose, constitutes about 41–43%. Next in abundance is hemicellulose, which is around 20% in deciduous trees but near 30% in conifers. It is mainly five-carbon sugars that are linked in an irregular manner, in contrast to the cellulose. Lignin is the third component at around 27% in coniferous wood vs. 23% in deciduous trees. Lignin confers the hydrophobic properties reflecting the fact that it is based on aromatic rings. These three components are interwoven, and direct covalent linkages exist between the lignin and the hemicellulose. A major focus of the paper industry is the separation of the lignin from the cellulose, from which paper is made. •In chemical terms, the difference between hardwood and softwood is reflected in the composition of the constituent lignin. Hardwood lignin is primarily derived from sinapyl alcohol and coniferyl alcohol. Softwood lignin is mainly derived from coniferyl alcohol.[22] •Extractives •Aside from the lignocellulose, wood consists of a variety of low molecular weight organic compounds, called extractives. The wood extractives are fatty acids, resin acids, waxes and terpenes.[23] For example, rosin is exuded by conifers as protection from insects. The extraction of these organic materials from wood provides tall oil, turpentine, and rosin. • WOOD –EXAMPLE OF STRUCTURE transversal sectional view January 2018/4_2 NATURAL POLYMERS MU SCI 4_2 2018 6 img648.jpg Anatomic Structure of the Coniferous species J – Tracheides of the Spring Wood, L - Tracheides of the Summer Wood, S – Pitchy tubule January 2018/4_2 NATURAL POLYMERS MU SCI 4_2 2018 7 WOOD BIOMASS Ammonia HYDROGEN Formaldehyde Methanol Methane Hydrocarbones Wood gas Wood oil Charcoal Gas Wheel grease Fuels & Chemicals Synthese gas Carbonizing Liquidizing Incineration Thermal energy Hydrolysis Glucose Xylose Molasses 2-furalaldehyde DECOMPOSITION Sulfate Sulfite Natron PROCESS Pulp Hemicelluloses Lignin Waste liquor Paper Cellulose fibres Cellulose Derivatives Saccharides Thermal energy The other routes of exploitation Pulping Mechanical wood pulp Paper Gasification Lignin WOOD AS THE CHEMICAL RAW MATERIAL WOOD GAS as CHEMICAL RAW MATERIAL & FUEL from RENEWABLE SOURCES January 2018/4_2 NATURAL POLYMERS MU SCI 4_2 2018 8 Component (% vol.) Mean value O2 in the Sample* 1,815 CO2 10,946 H2 18,600 CO 22,050 CH4 1,620 N2 44,000 Ar** 0,569 ethane 0,018 ethylene 0,128 The other components 0,254 SUM (Total) 100,000 What is possible to be used for production of the Wood gas? Which are the ADVANTAGES versus DISADVANTAGES of the Wood gas? Wood gas in the HISTORY? January 2018/4_2 NATURAL POLYMERS MU SCI 4_2 2018 9 Dřevoplyn auto 800px-Gengas_1944.jpg Manufacture of CELLULOSE •NATRON •SULFITE •SULFATE •WE GO THROUGT IT IN DETAIL LATER January 2018/4_2 NATURAL POLYMERS MU SCI 4_2 2018 10 Polyphenolic compounds January 2018/4_2 NATURAL POLYMERS MU SCI 4_2 2018 11 •Polyphenols are a Group of Chemical Compounds contained in Plants. They are characterized by Presence more then one Phenolic unit or building block in a Molecule. •Polyphenols are divided in general: –Hydrolysable tannins (esters of gallic acid and glucose or the other sachcarides) –Phenylpropanoides, e.g. lignins, –Flavonoids –Condensed tannins LIGNIN 1 January 2018/4_2 NATURAL POLYMERS MU SCI 4_2 2018 12 •The main NONcelullosis part of Wood (20 – 30 % w/w), coniferous tree has more Lignin then broad-leaved tree •It forms the adhesive component between celullose Fibres > WOOD is so the COMPOSITE MATERIAL! •Amorphous macromolecular substance , a Mixture of up to now not entirely revealed composition > there are many Formulas of Lignin (see the next slides) •Lignin is probably chemically bonded to POLYSACCHARIDES in the Wood •PHENYLPROPANE derivatives are considered as the Basic building unit of the Lignin • LIGNIN 2 January 2018/4_2 NATURAL POLYMERS MU SCI 4_2 2018 13 img633.jpg Derivatives of PHENYLPROPANE LIGNIN 3 January 2018/4_2 NATURAL POLYMERS MU SCI 4_2 2018 14 img641.jpg img642.jpg Crosslinking of lignin via ETHEREAL BRIDGE Derivatives PHENYLPROPANE creating LIGNIN LIGNIN 4 – POSSIBLE FORMULAS I January 2018/4_2 NATURAL POLYMERS MU SCI 4_2 2018 15 800px-Lignin.png LIGNIN 5 –POSSIBLE FORMULAS II January 2018/4_2 NATURAL POLYMERS MU SCI 4_2 2018 16 img643.jpg LIGNIN 6 – How is it gained? •LIGNIN is the WASTE MATERIAL at Production of the Chemical Production of the Pulp •Problem of its Utilisation is, that LIGNIN is not well defined Substance, but LIGNIN from various Sources is different as to the Composition •Reactive point is the Ethereal Bridge > the Possibility to produce Methanol via Cleavage • –OCH3 Group • • • January 2018/4_2 NATURAL POLYMERS MU SCI 4_2 2018 17 img638.jpg img634.jpg LIGNIN 7 – Problem of its Utilisation is, that LIGNIN is not well defined Substance, but LIGNIN from various Sources is different as to the Composition January 2018/4_2 NATURAL POLYMERS MU SCI 4_2 2018 18 img640.jpg The BASIC SUBSTANCES for various LIGNINS Grass LIGNIN Conifer tree LIGNIN Broad-leaved tree LIGNIN LIGNIN 8 – Chemical and other Utilisation •Chemical – it is up to now only the Minimal one • January 2018/4_2 NATURAL POLYMERS MU SCI 4_2 2018 19 img632.jpg Kyselina gallová Other Utilisation: The main part,so called „Waste liquor“, is combusted up to now VALORIZATION OF LIGNIN – CHEAP WASTE POLYMER IS WAITING FOR YOU! Vanillin Gallic acid LIGNIN 9 – Chemical and other Utilisation •Chemical – it is up to now only the Minimal one • January 2018/4_2 NATURAL POLYMERS MU SCI 4_2 2018 20 The very interesting Process of the Chemical Utilisation of LIGNIN has appeared last year on Internet. It should result up to terephthalic acid LIGNIN 10 – the LATEST LITERATURE It will be issued in 2018 or 2019 January 2018/4_2 NATURAL POLYMERS MU SCI 4_2 2018 21 BOOK LIGNIN VALORIZATION Anouncement001.jpg Emerging Approaches (RSC Publishing, Royal Society Chemistry) Editor: Gregg T Beckham Tannins •Tannins are the Plant Polyphenols of the bitter or/and astringent taste, coagulating proteins and alkaloids •Tannins are used for Vegetable tanning of Rawhide to Leather •Tannins are from the Chemical point of view big Polyphenolic Compounds, which contains hydroxyl and carboxyl Groups possessing ability to bound themselves to Proteins and other Macromolecules •Tannins have usually MW of approx. from 500 to 3 000 g/mol. January 2018/4_2 NATURAL POLYMERS MU SCI 4_2 2018 22 January 2018/4_2 NATURAL POLYMERS MU SCI 4_2 2018 23 img627.jpg Spruce Bark EXTRACTING Tannin Concentrated Solution Converting of Spruce Bark to Tannin Shredding Milling Sorting Water + NaHSO3 Extracted Bark Dewatering by Pressing Combustion or Agricultural Use Fining (Clarifying) & Filtration Vacuum thickening Drying Tannin Powder January 2018/4_2 NATURAL POLYMERS MU SCI 4_2 2018 24 375px-Tannic_acid_2-svg.png Tannin – one of the POSSIBLE STRUCTURES January 2018/4_2 NATURAL POLYMERS MU SCI 4_2 2018 25 800px-Tannic_acid.png Tannin – other of the POSSIBLE STRUCTURES January 2018/4_2 NATURAL POLYMERS MU SCI 4_2 2018 26 800px-Tannin_in_Plastic_container.jpg Tannin = tannic acid or digallic acid or gallotannic acid or gallotannin 800px-Bottle_of_tannic_acid.jpg January 2018/4_2 NATURAL POLYMERS MU SCI 4_2 2018 27 Product SIGMA ALDRICH Tannic acid 5 Products Synonym: Gallotannin, Tannin CAS Number: 1401-55-4 Empirical Formula (Hill Notation): C76H52O46 Molecular Weight: 1701.20 Beilstein Registry Number: 8186396 https://www.sigmaaldrich.com/content/dam/sigma-aldrich/structure9/023/mfcd00066397.eps/_jcr_content /renditions/mfcd00066397-large.png Properties Chemical formula C76H52O46 Molar mass 1701.19 g/mol Density 2.12g/cm3 Melting point decomposes above 200 °C Solubility in water 2850 g/L Solubility 100 g/L in ethanol 1 g/L in glycerol and acetone insoluble in benzene, chloroform, diethyl ether, petroleum, carbon disulfide, carbon tetrachloride. Acidity (pKa) ca. 10 January 2018/4_2 NATURAL POLYMERS MU SCI 4_2 2018 28 img624.jpg Hydrolysable tannins = Gallotannic acid + Bound saccharides Ellagic acid Gallic acid January 2018/4_2 NATURAL POLYMERS MU SCI 4_2 2018 29 img626.jpg Flavonoids > condensed tannins January 2018/4_2 NATURAL POLYMERS MU SCI 4_2 2018 30 Tannins derived from STILBENE img654.jpg img655.jpg 320px-Stilbene_trans_structure_svg.png Cis i trans January 2018/4_2 NATURAL POLYMERS MU SCI 4_2 2018 31 Flavonoids > condensed tannins & Hydrolysable tannins = Gallotannic acid & Ellagic acid +Bound saccharides & Tannins derived from STILBENE They are frequently occurring together in one Plant extract January 2018/4_2 NATURAL POLYMERS MU SCI 4_2 2018 32 img656.jpg Vegetable tanning of Rawhide to Leather Hydrogen bond Covalent bond Interaction of Tannins with Collagene Iron gall ink ink 1 •Iron gall ink (also known as iron gall nut ink, oak gall ink, and common ink) is the Ink purple-black colour, made from salts of Iron and taninn from plant sources. It is concerned organometallic compound dispersed in Water, in which is stabilized by the binding agent and this additive ensures remaining of the pigment Dispersion in the Solution. It currently used in Europe 12.Century since. January 2018/4_2 NATURAL POLYMERS MU SCI 4_2 2018 33 gallnut, gall-apple > 120px-Galle DUBĚNKA 08012018.jpg Iron gall ink ink 2 January 2018/4_2 NATURAL POLYMERS MU SCI 4_2 2018 34 •Simple Recipe •Tannin = tannic acid •Green vitriol (FeSO4) •ARABIC GUM > Plant gum •Water Iron gall ink ink 3 January 2018/4_2 NATURAL POLYMERS MU SCI 4_2 2018 35 Chemická reakce při vzniku duběnkového inkoustu Fe+2 Fe+3 Gallic acid Tannic acid Glucose Ferrous Gallic salt Ferric Gallic salt Iron gall ink 4 January 2018/4_2 NATURAL POLYMERS MU SCI 4_2 2018 36 •Chemical Basis of the Iron gall ink is as follows: •Reaction of the Iron Oxidation number/state Change ions’ from FERROUS (Fe2+) to FERRIC (Fe3+) state by atmospheric OXYGEN and via this way Change of the Colour from the Pale-grey solution to Purple-black •Chemical Basis of the Iron gall ink BLEACHING is as follows: •Reaction of the Iron Reduction from FERRIC (Fe3+) to FERROUS (Fe2+) •HOW TO REFRESH THE REDUCED FERROUS (Fe2+) ? •OXIDATION from FERROUS (Fe2+) to FERRIC (Fe3+) state •DURABILITY OF THE Iron gall ink is increased by the Reaction with Cellulose or Collagen Fe+3 Fe+2 January 2018/4_2 NATURAL POLYMERS MU SCI 4_2 2018 37 duběnkový inkoust 001.jpg duběnkový inkoust 002.jpg January 2018/4_2 NATURAL POLYMERS MU SCI 4_2 2018 38 duběnkový inkoust 003.jpg duběnkový inkoust 004.jpg INK versus China ink •INK is composed from: …………… •China ink is composed from : ……… January 2018/4_2 NATURAL POLYMERS MU SCI 4_2 2018 39 Tanins & Food Industry January 2018/4_2 NATURAL POLYMERS MU SCI 4_2 2018 40 • Clarifying of the Fruit juice in combination with Gellatin • It coagulate the Proteins Tanin – quite new Use January 2018/4_2 NATURAL POLYMERS MU SCI 4_2 2018 41 pěny z taninů 17102017.jpg polyestery 2 vyd 1978184.jpg It must be CROSSLINKED by something! Humin substances •Humin substances are natural organic substances arising by decomposition of mainly plants’ remains. •Humin substances are only difficult further decomposed and are contained in the Soil, Peat, Coal and some Water sources at very high Level. •Humin substances are divided according their solubility in Water to: •Humins, •Humine acids, •Fulvene acids. January 2018/4_2 NATURAL POLYMERS MU SCI 4_2 2018 42 Fulvene_with_hydrogens_svg WIKI ENG 08012017.png FULVENE Humin Acids 1 January 2018/4_2 NATURAL POLYMERS MU SCI 4_2 2018 43 •Humin acids are insoluble in Water at pH 2 and lower, but are soluble at higher pH. The Typical colour is brown to black-brown •Humin acids contain –OH and –COOH groups • • January 2018/4_2 NATURAL POLYMERS MU SCI 4_2 2018 44 huminové kyseliny001.jpg DEAD BIOMASS Tannin Saccharides & Polysaccharides Fats Proteins Other DEGRADATION & DECOMPOSITION Amino acids, aromatics, fatty acids, organic acids, phenols, saccharides and the other Chemical & Biochemical Condensation Complex Compounds Oligomeric Compounds Fulvene acids Subsequet Oligomerisation and Condensation Humin Compounds Humin acids Fulvene acids Humin Humin Acids 2 January 2018/4_2 NATURAL POLYMERS MU SCI 4_2 2018 45 huminové kyseliny002.jpg HYPOTHETICAL FORMULA of Humin Acids according to Stevenson (1992) Humin substances January 2018/4_2 NATURAL POLYMERS MU SCI 4_2 2018 46 •Humin substances are used mainly for the Plant nutrition. Although it is not a Fertilizer as it is usually meant (Material containing N, P, K), it enables easier intake of the Plant nutrition , stimulating formation of the Root system. Thank this the Plant is able to absorb better Water and nutrition. It promotes photosynthesis and improves the Soil properties. •Humin substances are supplied for agriculture use as the Solution, powders or pellets. They are able to be applied as a Spray, possibly combined with the other Fertilizers or Chemicals for Plant protection. • • 1. Generation of the Biodegradable synthetic plastics – Brown coal Humates I have worked with it! January 2018/4_2 NATURAL POLYMERS MU SCI 4_2 2018 47 •EXTRACTION FROM THE BROWN COAL – it is a Part, which is not enough transformed to Coal (lower carbon content) > It was a Dry dark brown powder solid. •What was the Target: •ADDITIVATION OF THE LDPE TO PRODUCE A BIODEGRABLE FILMS