NATURAL POLYMERS MU SCI 7/2 2018 1 NATURAL POLYMERS Polysaccharide II CELLULOSE 2 Dr. Ladislav Pospíšil January 18 2018 Cellulose is the most widespread BIOPOLYMER on Earth, up to 1,5×109 tons per annum is arising Time schedule January 18 2018 NATURAL POLYMERS MU SCI 7/2 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 Cellulose natural Abundance in WOOD January 18 2018 NATURAL POLYMERS MU SCI 7/2 2018 3 The only approx. 1/3 of the whole Tree is Cellulose, including a Root and a Tree stump! WOOD Polymeric Substances (90 – 97 % w/w) Associated Substances (3 – 10 % w/w) Polysaccharide Part HOLOCellulose AROMATIC Part LIGNIN (25 – 35 % w/w) Inorganic Substances Organic Substances Cellulose (45 – 50 % w/w) HEMICellulose Cellulose natural Abundance in WOOD–another Scheme January 18 2018 NATURAL POLYMERS MU SCI 7/2 2018 4 Polymeric Substances (90 – 97 % w/w) AROMATIC Part LIGNIN (18 – 28 % w/w) Polysaccharide Part HOLOCellulose (70 % w/w) Cellulose (40 – 47 % w/w) HEMICellulose & Polyuronide (20 – 30 % w/w) Polyuronide Pectine Wood Gums Alginate Real (Pure) HEMICellulose Occurrence of the Associated Substances in WOOD January 18 2018 NATURAL POLYMERS MU SCI 7/2 2018 5 Substance Saccharide Essential/ethereal oil (terpeny) Tannine Sterols (it belongs to TERPENOIDES) Inorganic Substances (Ash) Fats, Oils, Waxes Resinous Acids (e.g. Abietic Acid, which is a Part Resins) Proteins Aliphatic Acids Cellulose natural Abundance January 18 2018 NATURAL POLYMERS MU SCI 7/2 2018 6 Linters =short Cotton Fibers, which are not able to be spun to Thread PDM = MEAN DEGREE OF POLYMERIZATION Cellulose Sort (Source) PDM Cotton 1750 – 3356 Wood 650 – 1256 REGENERATED Cellulose 200 - 500 Chemical Composition of COTTON versus WOOD Component % w/w COTTON Linters Coniferous Tree Broad Leaf Tree HOLOCellulose 90 – 94 50 – 58 52 – 54 Pentosanes 1,5 – 2,0 11 25 Lignin 2,0 – 3,0 26 – 28 17 Pektines 2,0 1,0 1,5 – 2,0 Proteins 1,5 – 2,0 0,5 – 0,8 0,5 – 0,8 Fats & Waxes 0,5 – 1,0 1,0 – 2,0 1,0 2,0 Ash 1,0 0,25 – 0,5 0,25 HEMICellulose Polyuronide Hexosane Pentosane DEGRADATION of PAPER based on Cellulose 1 January 18 2018 NATURAL POLYMERS MU SCI 7/2 2018 7 papír DEGRADACE 18112017 004.jpg papír DEGRADACE 18112017 002.jpg papír DEGRADACE 18112017 003.jpg DEGRADATION of PAPER based on Cellulose 2 January 18 2018 NATURAL POLYMERS MU SCI 7/2 2018 8 papír DEGRADACE 18112017 005.jpg papír DEGRADACE 18112017 006.jpg DEACIDIFICATION of PAPER based on Cellulose 1 January 18 2018 NATURAL POLYMERS MU SCI 7/2 2018 9 papír ODKYSELOVÁNÍ 18112017 007.jpg January 18 2018 NATURAL POLYMERS MU SCI 7/2 2018 10 papír ODKYSELOVÁNÍ 18112017 008.jpg DEACIDIFICATION of PAPER based on Cellulose 2 January 18 2018 NATURAL POLYMERS MU SCI 7/2 2018 11 papír ODKYSELOVÁNÍ 18112017 009.jpg DEACIDIFICATION of PAPER based on Cellulose 3 PENTOSANE – an Example January 18 2018 NATURAL POLYMERS MU SCI 7/2 2018 12 PENTOSAN arabinoxylan GOOGLE 12112017.gif XYLANE - belongs to HEMICELULOSES img755.jpg PENTOSANE – an Example January 18 2018 NATURAL POLYMERS MU SCI 7/2 2018 13 MANAN - belongs to HEMICELULOSES MANNAN -Primary-structure-of-two-mannan-type-hemicelluloses-A-galactomannans-and-B Google Images 12112017.png Mannose WIKI CZ 12112017.png Manose MAIN of the Associated Substances in Cellulose 1 •Hemicelulose •Lignin •Essential/ethereal oil (terpeny) (in Wood) • January 18 2018 NATURAL POLYMERS MU SCI 7/2 2018 14 ! COTTON Fibres have almost no Hemicelluloses or LIGNIN ! LIGNIN - DETERMINATION January 18 2018 NATURAL POLYMERS MU SCI 7/2 2018 15 INTERNATIONAL NORM ISO/AWI Standard English Denomination Pulps -- Determination of lignin content -- Acid hydrolysis method Date of Issue Under development (18. 1. 2018) January 18 2018 NATURAL POLYMERS MU SCI 7/2 2018 16 The Rest to 100 % is probable HUMIDITY The Figures from different Sources could be a bit different, what is PROBABLY due to COTTON sort MAIN of the Associated Substances in COTTON Cellulose 1 Chemical Composittion of COTTON Component Content (% w/w) Cellulose 95,3 Saccharides 0,18 Reduced Saccharides 0,04 Nitrogen Compounds 0,17 Waxes 0,73 Pectines 1,20 Water extractable Compounds 3,07 Organic Acids 0,20 Ash 0,86 Cellulose & Associated Substances Concentration in COTTON Componenet Cellulose Pectines Proteins Waxes Ash Primary Wall 54 9 14 8 3 Secondary Wall 96 1 1,1 0,4 1,0 COTTON Fiber 94 1,2 1,3 0,6 1,2 Hemicelulose – what are composed of? 1 January 18 2018 NATURAL POLYMERS MU SCI 7/2 2018 17 img755.jpg img754.jpg The same Unit as the CELULOSE is January 18 2018 NATURAL POLYMERS MU SCI 7/2 2018 18 img756.jpg img757.jpg ATTENTION: this is FURANOSE! The five atoms Curcle only! Hemicelulose – what are composed of? 2 January 18 2018 NATURAL POLYMERS MU SCI 7/2 2018 19 img758.jpg img759.jpg Hemicelulose – what are composed of? 3 Hemicellulose January 18 2018 NATURAL POLYMERS MU SCI 7/2 2018 20 •There is approx. 17 – 41 % w/w of Hemicelulose in the Wood, more in the broad-leaved Trees •Polysaccharides with lower MEAN DEGREE OF POLYMERIZATION (approx. 100 – 200) •They are more easy to hydrolyse by both Acids and Bases •The short side Chains are frequently present •Hemicelluloses are sorted accordingly to their main building Components as follows: –Xylan (mostly broad-leaved Trees) –Mannan (mostly coniferous tree) –Galactan (mostly coniferous tree) • Hemicellulose January 18 2018 NATURAL POLYMERS MU SCI 7/2 2018 21 img753.jpg img752.jpg mostly broad-leaved Trees mostly coniferous tree CELLULOSE - Thermic Degradation 1 January 18 2018 NATURAL POLYMERS MU SCI 7/2 2018 22 CELULÓZA - TERMICKÁ DEGRADACE 002.jpg January 18 2018 NATURAL POLYMERS MU SCI 7/2 2018 23 Fig-2-Pyrolysis-curves-of-hemicellulose-cellulose-and-lignin-from-TGA-Adapted-with.png CELLULOSE - Thermic Degradation 2 Production of Cellulose I January 18 2018 NATURAL POLYMERS MU SCI 7/2 2018 24 WOOD Polymeric Substances (90 – 97 % w/w) Associated Substances (3 – 10 % w/w) Polysaccharide Part HOLOCellulose AROMATIC Part LIGNIN (25 – 35 % w/w) Inorganic Substances Organic Substances Cellulose (45 – 50 % w/w) HEMICellulose Seed Fibres Bast/Stalk Fibres Cotton Fibres Kapok Fibres Coconut Fibres Flax Fibres Hemp Fibres Jute Fibres Ramie Fibres Kenaf Fibres Leaf Fibres Sisal Fibres Manila Hemp Fibres Pineapple Fibres Production of Cellulose II •Seed Fibres – Cotton > the Harvesting and Cleaning are only necessary • The Fibre has already •Sufficient Fineness •(tex, denier), • it is Fibre diameter • • •Fibre length and Fineness •Are different according •to Place of growing •(Egypt, Asia) • January 18 2018 NATURAL POLYMERS MU SCI 7/2 2018 25 January 18 2018 NATURAL POLYMERS MU SCI 7/2 2018 26 plant_cotton-field.jpg plant_cotton-plant.jpg Cotton Field Harvesting by Hand or by Machine Cotton entered Europe during 18. and 19. Centuries Morphology of the Cellulose Fibre 1 January 18 2018 NATURAL POLYMERS MU SCI 7/2 2018 27 img312.jpg Zkroucení „do vrtule“ 1) Cotton Seed, 2) Fibre, 3) Skin, 4) Primary Wall (approx. 0,1 mm), 5) Secondary Wall (approx. 4 mm), 6) Change of Fibrils’ Turning, 7) Lumen, 8) Fibre after lost of Water Morphology of the Cellulose Fibre 2 January 18 2018 NATURAL POLYMERS MU SCI 7/2 2018 28 img154.jpg cellulose 91.00% water 7.85% protoplasm, pectins 0.55% waxes, fatty substances 0.40% mineral salts 0.20% Primary Wall Secondary Wall Tertiary Wall Morphology of the Cellulose Fibre 3 January 18 2018 NATURAL POLYMERS MU SCI 7/2 2018 29 BAVLNA 1.jpg BAVLNA 2.jpg 1) Primary Wall (approx. 0,1 mm), 2) Outer Part of Secondary Wall (approx. 4 mm), 3) Middle Part of Secondary Wall 4) Inner Part of Secondary Wall Lumen, 5)Chanel with Rest of the Protoplasm SCHEMA OF THE ARRAGAMENT OF THE COTTON WALLS 1) Primary Wall, 2) Outer Part of Secondary Wall, 3) Middle Part of Secondary Wall January 18 2018 NATURAL POLYMERS MU SCI 7/2 2018 30 PROPERTIES OF THE COTTON SINGLE FIBER Fairly uniform in width, 12–20 micrometers; length varies from 1 cm to 6 cm (½ to 2½ inches); typical length is 2.2 cm to 3.3 cm (⅞ to 1¼ inches). SEM VLÁKEN C21a.jpg cellulose 91.00% water 7.85% protoplasm, pectins 0.55% waxes, fatty substances 0.40% mineral salts 0.20% SEM, Magnification approx. 1000x Morphology of WOOD 1 January 18 2018 NATURAL POLYMERS MU SCI 7/2 2018 31 buňka dřeva 1.jpg buňka dřeva 2.jpg O – middle Lamella (LIGNIN) I – Primary Wall (P) II – Secondary Wall (S) III –Tertiary Wall (T) L – Cell lumen (Air) L B L – Cell lumen (Air)) SL – middle Lamella (LIGNIN) P – Primary Wall S1, S2 – Secondary Wall T (S3) – Tertiary Wall B – warted Layer Morphology of WOOD 2 January 18 2018 NATURAL POLYMERS MU SCI 7/2 2018 32 buňka dřeva 3.jpg buňka dřeva 4.jpg Pay Attention to: • DIFFERENT Fibrils Orientations in DIFFERENT Walls S1, S2 a S3 Tracheids Morphology of Cellulose Fibre 4 January 18 2018 NATURAL POLYMERS MU SCI 7/2 2018 33 BAVLNA 3.jpg OLD Units • p = pond = g*9,81 = 0,0098 N = 0,98 cN SI Units • cN dtex-1 = cca. p dtex-1 dtex = Mass of the 10 km of Fibre expressed in grams (g) Fibre Length Fibre thickness Tensile Strength at Dry Tensile Strength at Wet Ductility Density Moisture Content Textile Units! Cellulose Production III •Herb (Plant) Bast/Stalk – Flax, Hemp, Jute •It is necessary to remove BIOLOGICALY Pectins and then to remove Wooden Part of the Stalk •Fibre is long, but rough •Tensile Strength is higher then Cotton •It is necessary to fine the Fibres for Textile utilisation •Yield rate of Fibre is low, approx. 10 % w/w of the Whole Plant January 18 2018 NATURAL POLYMERS MU SCI 7/2 2018 34 Flax = Plant Linen = Fibre Flax Stalk – CROSSCUT January 18 2018 NATURAL POLYMERS MU SCI 7/2 2018 35 http://www.rootsweb.ancestry.com/~belghist/Flanders/Picts/flaxStem.gif The stem varies from 60 to 120 cm in length and consists of fiber bundles lying between the outer BARK and a WOODY CORE. The INDIVIDUAL FIBERS, 10 to 40, are held together in the bundles by PECTINS. The bundles lie around the core and are attached to it and one another by pectins. C:\Users\ladapospa\Documents\Lada\Přírodní polymery MU 2013\POLYSACHARIDY (mimo škrob)\PEKTIN 15012016.jpg Structure Formula of PECTIN R = H or –CH3 January 18 2018 NATURAL POLYMERS MU SCI 7/2 2018 36 plant_03_DRa157 LEN.jpg plant_03_DRb042 LEN ROSENÍ.jpg FLAX is in Bloom Dew-retting of Flax on the Field Flax is harvested in Europe from the Turn of Millennium since Cellulose Production III B HISTORICAL Method of Linen gaining January 18 2018 NATURAL POLYMERS MU SCI 7/2 2018 37 http://www.rootsweb.ancestry.com/~belghist/Flanders/Picts/scutchingTool2.gif http://www.rootsweb.ancestry.com/~belghist/Flanders/Picts/flaxHackling.gif CURRENT Industrial Method of Linen gaining January 18 2018 NATURAL POLYMERS MU SCI 7/2 2018 38 Zpracování lnu 30112016.jpg Flax Processing Scutching Heckling Brokening Long Fibres Flax scotch Flax Tow Heckled Tow January 18 2018 NATURAL POLYMERS MU SCI 7/2 2018 39 LEN stonek, vlákno, tkanina Textielmuseum-cabinet-02 WIKI ENG 30112016.jpg Flax & Linen: • Stalk, • Fiber, • Weaving yarn, • Fabric January 18 2018 NATURAL POLYMERS MU SCI 7/2 2018 40 PAZDEŘÍ 1280px-Hemp_shives WIKI CZ 30112016.jpg Hemp scotch January 18 2018 NATURAL POLYMERS MU SCI 7/2 2018 41 PAZDEŘOVÁ DESKA KONOPÍ 1280px-Spanplatte WIKI CZ 30112016.jpg Hemp scotch Board It has the better Mechanical Properties then Wood Fibres one January 18 2018 NATURAL POLYMERS MU SCI 7/2 2018 42 LNĚNÁ KOUDEL WIKI CZ 30112016.jpg Flax scotch KONOPNÁ KOUDEL1280px-Hennepvezel_Cannabis_sativa_fibre WIKI CZ 30112016.jpg Hemp scotch The similar Fibres, but Hemp has different Colour Cellulose Production IV – WOOD January 18 2018 NATURAL POLYMERS MU SCI 7/2 2018 43 •Natronový postup s NaOH (listnaté dřevo, sláma, odpad) •Sulfitový postup (smrk, listnaté dřevo) •Sulfátový postup (buk, bříza, borovice, sláma, odpad) •Výtěžky jsou jen cca. 25 % hmot. (údaje se liší podle zdroje i podle typu dřeva) z celkové ve dřevě obsažené celulóze • January 18 2018 NATURAL POLYMERS MU SCI 7/2 2018 44 •5 – 12 % NaOH •150 – 180 °C •700 – 1000 kPa •3 – 6 hodin Soda pulping is a chemical process for making wood pulp with sodium hydroxide as the cooking chemical. In the Soda-AQ process, anthraquinone (AQ) may be used as a pulping additive to decrease the carbohydrate degradation. The soda process gives pulp with lower tear strength than other chemical pulping processes (sulfite process and kraft process), but has still limited use for easy pulped materials like straw and some hardwoods.[1] January 18 2018 NATURAL POLYMERS MU SCI 7/2 2018 45 •Ca(HSO3)2, SO2 •130 °C •300 – 400 kPa •3 – 6 hodin • img295.jpg The sulfite process produces wood pulp which is almost pure cellulose fibers by using various salts of sulfurous acid to extract the lignin from wood chips in large pressure vessels called digesters. The salts used in the pulping process are either sulfites (SO32−), or bisulfites (HSO3−), depending on the pH. The counter ion can be sodium (Na+), calcium (Ca2+), potassium (K+), magnesium (Mg2+) or ammonium (NH4+). It is possible to substitute Ca+2 by Mg+2 or by NH4+ Sulphate Process January 18 2018 NATURAL POLYMERS MU SCI 7/2 2018 46 •Na2SO4, Na2CO3, Na2S, Na OH •150 – 180 °C •700 – 1000 kPa •3 – 6 hodin • img296.jpg It is possible to get back from the Melt of the NaS, but most importantly Na2CO3, which is Caustificied as follows: The new Cooking Liquor is possible to get via this Procedure The Sulphate Process is suitable to be employed for all Kinds of Wood and has the Best Economy of Cellulose Production DELIGNIFICATION of Wood by DEPOLYMEROISATION Sulfate Process 8. 11. 2017 PŘÍRODNÍ POLYMERY CELULÓZA PŘF MU 7 2017 47 Depolymerisation of lignin WIKI ENG 19012018.png January 18 2018 NATURAL POLYMERS MU SCI 7/2 2018 48 Pulp_mill_2 WIKI ENG 19012018.jpg White Liquor Sulphate Process Utilisation of Cellulose (Pulp) January 18 2018 NATURAL POLYMERS MU SCI 7/2 2018 49 •The pulp papermaking process •Textile Production •Pharmacy •Regenerated Cellulose •DERIVATIVES of CELLULOSE –Esters –Nitrates –Alkyl (aryl)cellulose –Carboxymethylcellulose –Hydroxyethylcellulose – The pulp papermaking process January 18 2018 NATURAL POLYMERS MU SCI 7/2 2018 50 •Paper is a thin material produced by pressing together moist fibres of cellulose pulp derived from wood, rags or grasses, and drying them into flexible sheets. •Paper is the Sheet Material with having the Weight up to 250 g/m2, made of Fibres and the Additives, which determine its Specification. •Cardboard and Paperboard > 250 g/m2 The pulp papermaking process January 18 2018 NATURAL POLYMERS MU SCI 7/2 2018 51 •PAPÍR • BUNIČINA 722px-Zellstoff_200_fach_Polfilter.jpg 800px-PaperAutofluorescence.jpg Pulp 200x Paper 800x The wood pulp papermaking process January 18 2018 NATURAL POLYMERS MU SCI 7/2 2018 52 •Mechanical wood pulp – mechanical Wood Pulping & Fibre Sorting & Bleaching >>> Lowcost Papers,e.g. Newspapers and Lavatory Paper • 800px-Mechanicalpulping.png January 18 2018 NATURAL POLYMERS MU SCI 7/2 2018 53 JUTA z Hladík Textilní vlákna.jpg Stalk Fiber 1 Jute, Magnification 180x January 18 2018 NATURAL POLYMERS MU SCI 7/2 2018 54 Stalk Fibers 2 & 3 LEN a KONOPÍ z Hladík Textilní vlákna.jpg Flax, Magnification 180x Hemp, Magnification 180x January 18 2018 NATURAL POLYMERS MU SCI 7/2 2018 55 LEAF FIBER 1 – SISAL NATIVE sisal puvodni 200x.jpg January 18 2018 NATURAL POLYMERS MU SCI 7/2 2018 56 LEAF FIBER 1 – SISAL NATIVE sisal puvodni 1kx b.jpg January 18 2018 NATURAL POLYMERS MU SCI 7/2 2018 57 LEAF FIBER 3 – SISAL AFTER EXPOSURE IN OUDOOR approx. 3years sisal degradovany 200x.jpg January 18 2018 NATURAL POLYMERS MU SCI 7/2 2018 58 LEAF FIBER 3 – SISAL AFTER EXPOSURE IN OUDOOR approx. 3 years sisal degradovany 1kx.jpg January 18 2018 NATURAL POLYMERS MU SCI 7/2 2018 59 LEAF FIBER 4 – SISAL Influence of the Outdoor Exposure EXPOZICE sisal degradovany 1kx.jpg In the Outdoor approx. 3 years sisal puvodni 1kx b.jpg NATIVE Magnification 1000x, SEM January 18 2018 NATURAL POLYMERS MU SCI 7/2 2018 60 LEAF FIBER 4 – SISAL Influence of the Outdoor Exposure EXPOZICE sisal degradovany 200x.jpg sisal puvodni 200x.jpg In the Outdoor approx. 3 years NATIVE Magnification 200x, SEM