NATURAL POLYMERS MU SCI 7 2018 1 NATURAL POLYMERS Polysaccharide II CELLULOSE 1 Dr. Ladislav Pospíšil January 7/2018 Cellulose is the most widespread BIOPOLYMER on Earth, up to 1,5×109 tons per annum is arising Time schedule January 2018/6 NATURAL POLYMERS MU SCI 6 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 January 7/2018 NATURAL POLYMERS MU SCI 7 2018 3 LITERATURE 1 Cellulose Literature 001.jpg Cellulose Literature 002.jpg Cellulose Literature 003.jpg Cellulose Literature 004.jpg January 7/2018 NATURAL POLYMERS MU SCI 7 2018 4 LITERATURE 2 Cellulose Literature 005.jpg Cellulose Literature 006.jpg Cellulose Literature 007.jpg Cellulose Literature 008.jpg January 7/2018 NATURAL POLYMERS MU SCI 7 2018 5 LITERATURE 3 Cellulose Literature 009.jpg Cellulose Literature 010.jpg Cellulose Literature 011.jpg January 7/2018 NATURAL POLYMERS MU SCI 7 2018 6 LITERATURE 4 Cellulose Literature 013.jpg Cellulose Literature 014.jpg Cellulose Literature 015.jpg January 7/2018 NATURAL POLYMERS MU SCI 7 2018 7 LITERATURE 5 Cellulose Literature 016.jpg Cellulose Literature 017.jpg Cellulose ISSN: 0969-0239 (Print) 1572-882X (Online) Description Cellulose is an international journal devoted to the dissemination of research and scientific and technological progress in the field of cellulose and related naturally occurring polymers. The journal is concerned with the pure and applied science of cellulose and related materials, and also with the development of relevant new technologies. This includes the chemistry, biochemistry, physics and materials science of cellulose and its sources, including wood and other biomass resources, and their derivatives. Coverage extends to the conversion of these polymers and resources into manufactured goods, such as pulp, paper, textiles, and manufactured as well natural fibers, and to the chemistry of materials used in their processing. Cellulose publishes review articles, research papers, and technical notes. hide Cellulose is an international journal devoted to the dissemination of research and scientific and technological progress in the field of cellulose and related naturally occurring polymers. The journal is concerned with the pure and applied science of cellulose and related materials, and also with the development of relevant new technologies. This includes the chemistry, biochemistry, physics and materials science of cellulose … 1.Cellulose Chemistry 2.Supramolecular stucture of Cellulose 3.Natural abundance of Cellulose 4. Solubility of Cellulose 5. Production of Cellulose 6. Use of Cellulose 7. Modification of Cellulose 8. Nanocellulose January 7/2018 NATURAL POLYMERS MU SCI 7 2018 8 January 7/2018 NATURAL POLYMERS MU SCI 7 2018 9 Natural Fibres Plant (Cellulose) Fibres Seed Fibres Bast/Stalk Fibres Leaf Fibres Flax Fibres Hemp Fibres Jute Fibres Ramie Fibres Kenaf Fibres Cotton Fibres Kapok Fibres Coconut Fibres Sisal Fibres Manila Hemp Fibres Pineapple Fibres Animal (Proteine) Fibres Inorganic Fibres Asbestos Fibres Insects Fibres Natural Silk Fibres Vertebrate Animal Hair Fibres Wool Fibres Angora wool Camel wool Etc. January 7/2018 NATURAL POLYMERS MU SCI 7 2018 10 D-glucose-chain-2D-Fischer.png img462.jpg img463.jpg January 7/2018 NATURAL POLYMERS MU SCI 7 2018 11 1280px-Ethyl-glucoside.png Formation of the Glykosidic Bond (Linkage) HEMIACETAL Formation A glycosidic bond is formed between the hemiacetal or hemiketal group of a saccharide (or a molecule derived from a saccharide) and the hydroxyl group of some compound such as an alcohol. A substance containing a glycosidic bond is a glycoside. HEMIACETAL is able further react with another nucleophilic Group and so form ACETAL and to eliminate Water. acetal When is the further Reagent a Saccharide whit suitable –OH Group, the POLYSACHARIDE is step by step forming Cellulose Ø ß-D-Glucose, ß-1,4 glycosidic Bond Ø It forms the structure Skeleton of Plants Ø It is not cleaved by Humans celulosa January 7/2018 12 NATURAL POLYMERS MU SCI 7 2018 Bond struktura CELULÓZA 1.jpg January 7/2018 13 NATURAL POLYMERS MU SCI 7 2018 C1 C4 b C1 C4 a img462.jpg img463.jpg Maltose is the repeating unit of STARCH: a(1-4) dimer of GLUCOSE Cellobiose is the repeating unit of CELLULOSE: b(1-4) dimer of GLUCOSE January 7/2018 14 NATURAL POLYMERS MU SCI 7 2018 struktura CELULÓZA 2.jpg struktura CELULÓZA004.jpg Linear Structure of CELLULOSE Cellobiose January 7/2018 NATURAL POLYMERS MU SCI 7 2018 15 img485.jpg Maltose is the repeating unit of STARCH: a(1-4) dimer of GLUCOSE Cellobiose is the repeating unit of CELLULOSE: b(1-4) dimer of GLUCOSE Survey of the most important disaccharides maltosa Maltose § Product of the Starch molecule Cleavage sacharosa Saccharose laktosa Lactose § beet-sugar, cane-sugar § no reducing The Bond arose via Hemiacetal HYDROXYLS from both constituent Parts Reducing Sugars January 7/2018 16 NATURAL POLYMERS MU SCI 7 2018 The Bond arose via Hemiacetal HYDROXYL from one constituent Molecule and NON Hemiacetal HYDROXYL from the other constituent Molecule January 7/2018 NATURAL POLYMERS MU SCI 7 2018 17 The Path from GLUKOSE to MALTOSE and finally to STARCH str 156.jpg str 157.jpg AMYLOPEKTIN.jpg H January 7/2018 NATURAL POLYMERS MU SCI 7 2018 18 glukóza celobióza CELULÓZA 2.jpg glukóza celobióza CELULÓZA 3.jpg str 157.jpg The Path from GLUKOSE to CELLOBIOSE and finally to CELLULOSE Cellulose Chemistry I/1 •Cellulose belong to the Polysaccharides •Cellulose form the main Part of the BIOMASS •Poly-(b-D-glucose) (Simplified Name) •Poly-1,4-b-D-glucopyranoyl-D-glucopyranose • January 7/2018 NATURAL POLYMERS MU SCI 7 2018 19 cellobiosa & celulosa.jpg C4 C1 January 7/2018 NATURAL POLYMERS MU SCI 7 2018 20 str 197.jpg Cellulose Chemistry I/2 It is the REDUCING FORM, but due to very low Concentration (the Macromolecule End Group only) CELLULLOSE is only very low reducing Polysaccharide Beginning Segment Final Segment January 7/2018 NATURAL POLYMERS MU SCI 7 2018 21 Cellulose Chemistry I/3 CELLULOSE is the High REDUCING POLYSACCHARIDE AFTER HYDROLYSE to GLUCOSE ONLY (ß-D-GLUCOSE ) img463.jpg January 7/2018 NATURAL POLYMERS MU SCI 7 2018 22 Cellulose Chemistry I/4 CELLULOSE as the reducing Polysaccharide is used for DEGREE OF POLYMERIZATION DETERMINATION BY END GROUPS METHOD, but which is assumed as LOW PRECISSE img463.jpg Cellulose Chemistry II January 7/2018 NATURAL POLYMERS MU SCI 7 2018 23 řetězec celilózy rozměry.jpg Revision is necessary! January 7/2018 NATURAL POLYMERS MU SCI 7 2018 24 vodíkové můstky - příklady z literatury.jpg • Hydrogen Bonds DO NOT HAVE Strength as high as classical Chemical Bond has. • Hydrogen Bonds are easy broken. • The new such Bond are restored immediately afterwards and there is Steady Association degree via Hydrogen Bonds at given Temperature Hydrogen Bonds in Liquids: a) Alcohol, b) Organic Acid, 3) Water Cellulose Chemistry III/1 January 7/2018 NATURAL POLYMERS MU SCI 7 2018 25 molekula celulózy.jpg Hydrogen Bonds are as inside one Molecule, so between two neighbouring Molecules Secondary Structure (Interaction in one Macromolecule Chain) Tertiary Structure (Interaction between two or more Macromolecule Chain) Cellulose Chemistry III/2 January 7/2018 NATURAL POLYMERS MU SCI 7 2018 26 Cellulose_strand_svg.png Once more Interactions both in one Macromolecule Chain and between two or more Macromolecule Chain) Cellulose Chemistry IV January 7/2018 NATURAL POLYMERS MU SCI 7 2018 27 img725.jpg P = M/162 Mean Mw (other Source accordingly) Cotton 1,78 – 2,43 x 106 Sulfite Cellulose 0,60 x 106 Viscose Fibres 0,23 x 106 ANOTHER SOURCE (P): •Cotton 15 000 •Sulfite Cellulose 5 – 9000 •Viscose Fibres 300 Short Fibers in the Cotton, which are not able to be spun to Thread (Waste Fibers, employed for the Chemical POLYMERANALOGIC MODIFICATION of Cellulose ) Cellulose DEGREE OF POLYMERIZATION – NATIVE Cellulose Raw Cotton Linters Flax Ramie Nettle Sulfite Cellulose DEGREE OF POLYMERIZATION DISTRIBUTION – AN EXAMPLE ONLY! January 7/2018 NATURAL POLYMERS MU SCI 7 2018 28 Alpha, beta and gamma celluloses have the same chemical structure, but celiluloses differ polymerisation degree (DP) and celluloses have diffrent solubility in 17,5% NaOH. Alpha cellulose doesn't dissolve in 17,5% NaOH and DP above 200. Beta cellulose dissolve in 17,5% NaOH and DP 30-200, but we can precipitated again from NaOH solution. Gamma cellulose dissolve in 17,5% NaOH and DP 10-30, but we can't precipitated again from NaOH slolution The alpha-cellulose is usually measure with the TAPPI's methods, but not the beta and gamma celluloses. I suppose that the alpha is the most plentiful of these ones but I am interested to know what is the difference between these celluloses according to their chemical structure. Cellulose Chemistry III b January 7/2018 NATURAL POLYMERS MU SCI 7 2018 29 str 160.jpg In GENERAL: • Bast Fibre and Cotton > HIGH P, • Woody plant – LOWER P, • REGENERATED Cellulose - LOW P Linters =short Cotton Fibers, which are not able to be spun to Thread Raw Cotton Linters Flax Ramie Nettle Sulfite Cellulose DEGREE OF POLYMERIZATION of various Celluloses Cellulose P Cellulose P Ramie 3 500 – 4 600 Pine 1 000 – 1 200 Egyptian Cotton 3 000 – 4 000 Viscose Fibres 250 – 800 Linters Approx. 1 400 a- Cellulose >200 Linters boliled off 1 200 – 1 300 b- Cellulose 30 - 200 Linters bleached Approx. 700 g- Cellulose 10 - 30 Beech 1 200 – 1 400 Beech bleached 700 – 1 300 Poplar 1 200 – 1 400 Straw Approx. 800 Cellulose Chemistry IV •The Figures of MW and P are different in different Source, except for COTTON •What could be the Reason: –Various Natural Sources, –Various viscose Fibre Grades (VERY PROBABLY), –Various Measurement Methods •What is usually missing: –MWD –Given of type MW (Mn or Mw) – January 7/2018 NATURAL POLYMERS MU SCI 7 2018 30 CELLULOSE PHYSICS I •DENSITY approx. 1,5 g/cm3 –This is an Effect of heteroatoms > higher Density then most of the SYNTHETIC POLYMERS (an Exception is e.g. PVC, PET and PA) –The Effect of Crystallinity > higher Density then Amorphous Parts of Macromolecules • •TENSILE STRENGHT approx. 300 Mpa –The Effect of an Fibre Orientation and Crystallinity –The TENSILE STRENGHT is LOWER at wet Conditions > the Effect of Water on Lowering an Interaction between a Fibrils, formed by Macromolecules •WATER SORPTION is high approx. 7 % w/w at 20 °C a 65 % RH (relative Humidity) January 7/2018 NATURAL POLYMERS MU SCI 7 2018 31 Cellulose Solubility January 7/2018 NATURAL POLYMERS MU SCI 7 2018 32 Solvent Solubility Associated Process Water Insoluble Water Sorption, without Change of Pn Solutions of some inorganic Salts (ZnCl2, AlCl3, SnCl4 etc.) Soluble Part Hydrolysis >Change of Pn Inorganic Acids (HCl, H2SO4, H3PO4 etc.) Soluble Part Hydrolysis >Change of Pn Hydroxides of alkalic Metals Soluble Alcoholates Formation Amine Complexes – Schweitzers Reagent Soluble Copper complexes formation Alkylamines Soluble I do not know Cellulose Solubility in 17,5 % w/w NaOH Water Solution after Wood delignification January 7/2018 NATURAL POLYMERS MU SCI 7 2018 33 Solvent 17,5 % w/w NaOH Water Solution Solubility Associated Process a Cellulose Insoluble b Cellulose Soluble By Acidification of Filtrate by Acetic Acid precipitate from the Solution Chains having Pn > 200, arisen during Delignification g Cellulose Soluble It remains in the Solution after Precipitation b cellulose and it is necessary to precipitate it using EtOH. It contains HEMICELLULOSES. Cellulose Solubility in 17,5 % w/w NaOH Water Solution after Wood delignification – INTERNATIONAL NORM January 7/2018 NATURAL POLYMERS MU SCI 7 2018 34 INTERNATIONAL NORM ISO 692 English Denomination Determination of alkali solubility Date of Issue 1.10.1993 Melting Points & Solubility of Saccharides and Cellulose January 7/2018 NATURAL POLYMERS MU SCI 7 2018 35 You can find also other Figures related to Temperature of Cellulose Decomposition! It is given by: • Air or Inert Gas (Nitrogen, Helium etc.), • Presence of the transition Valence Elements (mainly Fe+3, Mn+2, Co+2 etc.), which catalyse this Oxidation Substance Melting point (°C) Solubility in Water (% w/w) Glucose 146 Approx. 909 - 1 200 g/L Cellobiose 203 (Decomposition) Approx. 12 g/L Cellotriose 238 (Decomposition) ??? 25 - 50 Cellotetrose 251 (Decomposition) ??? 12,5 - 25 Cellopentose > 226 (Decomposition) 5 Cellulose 270 (Decomposition) Insoluble STARCH versus CELLULOSE I January 7/2018 NATURAL POLYMERS MU SCI 7 2018 36 img672.jpg STARCH is Polymer of a-D-glukopyranose CELULLOSE is Polymer of b-D-glukopyranose January 7/2018 NATURAL POLYMERS MU SCI 7 2018 37 img724.jpg STARCH (linear AMYLOSE) versus CELLULOSE II STARCH is Polymer of a-D-glukopyranose CELULLOSE is Polymer of b-D-glukopyranose January 7/2018 NATURAL POLYMERS MU SCI 7 2018 38 img749.jpg img748.jpg Strong Interactions via Hydrogen Bonds Other Possibility to represent Cellulose January 7/2018 NATURAL POLYMERS MU SCI 7 2018 39 struktura CELULÓZA003.jpg Strong Interactions via Hydrogen Bonds January 7/2018 NATURAL POLYMERS MU SCI 7 2018 40 Supermolecular Structure of Cellulose I micely celulźy.jpg Colourless inert Substance Insoluble in Water , Density 1,55 g/cm3 Space between the Microfibrils is filled by HEMICELLULOSE & LIGNIN AMORPHOUS CELLULOSE: • easy to swell • is more reactive than the crystalline one Hierarchy of STRUCTURES in CELLULOSE: • Macromolecule, • Microfibril, • Fibril, • LAMELAE. Microfibril crystalline AMORPHOUS Micellar Intermicellar REGIONS January 7/2018 NATURAL POLYMERS MU SCI 7 2018 41 Supermolecular Structure of Cellulose II Strong Interactions via Hydrogen Bonds vodíkové můstky v celióze.jpg Native Cellulose Swollen Cellulose Colloidal Solution of Cellulose January 7/2018 NATURAL POLYMERS MU SCI 7 2018 42 Supermolecular Structure of Cellulose III nadmolekulární struktura celulózového vlákna.jpg A – B > Crystalline Part C – D > Amorphous Part 8 Crosscut through the CrystallinePart 9 Crosscut through the Amorphous Part, which is PARTLY (LENGTHWISE) ORIENTED > NEMATIC STRUCTURE 10 Bundle (ELEMENTARY FIBRIL, MICROFIBRIL) MADE OF SEVERAL MACROMOLECULES MICROFIBRIL: • THICKNESS is usually 3 – 30 nm • LENGTH is usually Units of Microns January 7/2018 NATURAL POLYMERS MU SCI 7 2018 43 Crystalline Structure of Cellulose I img744.jpg img743.jpg Strong Interactions via Hydrogen Bonds Basic Cell of Cellulose Crystal lattice of Cellulose with marked Hydrogen Bonds January 7/2018 NATURAL POLYMERS MU SCI 7 2018 44 Crystalline Structure of Cellulose II img746.jpg img747.jpg I – Native Cellulose II – REGENERATED Cellulose III – It is formed via Action of Ammoniac or Amine on I or II Cellulose IV –by Heat Treatment + Glycerine on I or II Cellulose X – via Action of HCl, H2SO4, H3PO4 Scheme of Transition between Individual Polymorphid Forms of Cellulose