NATURAL POLYMERS MU SCI 2 2018 1 NATURAL POLYMERS ACID’S DERIVATIVES, NATURAL RESINS, DRYING OILS, SHELACK ETC. Dr. Ladislav Pospíšil January 2018/2 Time schedule January 2018/2 NATURAL POLYMERS MU SCI 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 – cellulose 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 Products •Natural Products –Renewable Sources –UNRENEWABLE SOURCE •Modified Natural Products •Synthetic Products •Why do we put the Oils in the Natural Polymers ? •POLYMERS arising by radical Reaction from some of the Natural Oils January 2018/2 NATURAL POLYMERS MU SCI 2 2018 3 Fats & Oils •Vegetable Fats (Oils) –Glycerides –Higher Fatty acids ( > 10 C Atoms) •Saturated •Unsaturated –One double Bond –More then one double Bond »Isolated »Conjugated » January 2018/2 NATURAL POLYMERS MU SCI 2 2018 4 img480.jpg OILS •Oil is a Liquid constituted (composed) of the Molecules, which comprise the hydrophobic hydrocarbon Chains. So they are not soluble (are INSOLUBLE) in the Water. They have lower Density then the Water has. •Food, edible Oils are the Vegetable liquid TRIGLYCERIDES. They can have one or more unsaturated Bonds between the Carbon Atoms. The more has the such Oil of the unsaturated Bonds between the Carbon Atoms, the less is its Viscosity. •Technical Grade Oils are mostly based on the utilisation of the so called MINERAL OILS, which are the Mixture of the HYRDOCARBONS manufactured by the Crude Oils Processing. The next Group of the Technical Grade Oils are the SILICONE OILS, which are manufactured by Synthesis (Polymerisation) from the Silicon based monomers. • January 2018/2 NATURAL POLYMERS MU SCI 2 2018 5 Glycerides of the Higher Fatty acids ( > 10 C Atoms) 1 January 2018/2 NATURAL POLYMERS MU SCI 2 2018 6 •How to characterise in Practice the Unsaturation •of the Higher Fatty acids •IodineVALUE – Determination according to prof. Hanush • • REACTION: -C=C- + IBr -C=C- I Br IBr + KI I2 + KBr I2 + 2Na2SO4 2 NaI + Na2S4O6 The IODINE VALUE (or IODINE ADSORPTION VALUE or IODINE NUMBER or IODINE INDEX) Glycerides of the Higher Fatty acids ( > 10 C Atoms) 2 January 2018/2 NATURAL POLYMERS MU SCI 2 2018 7 • • The FATS are dividing the IODINE VALUE (IV) accordingly: • Drying Oils – IN > 120 % w/w • Half Drying Oils – IN > 60 - 120 % w/w • NON Drying Oils – IN < 60 % w/w Fat (Oil) Iodine Value (% w/w) Cow Butter 26 – 40 Beef Tallow melted 40 – 48 Pig Lard 53 – 77 Ricin Oil 81 – 90 Peanut/Groundnut Oil 84 – 100 Oilseed rape Oil 94 – 106 Soybean (Soy bean) Oil 114 – 138 Suflower Oil 127 – 136 Linseed/Flaxseed Oil 170 - 204 EN ISO STANDARDS •EN ISO 660 •Animal and vegetable fats and oils - Determination of acid value and acidity •EN ISO 3961 •Animal and vegetable fats and oils - Determination of iodine value • EN ISO 3657 •Animal and vegetable fats and oils - Determination of saponification value • • • • January 2018/2 NATURAL POLYMERS MU SCI 2 2018 8 January 2018/2 NATURAL POLYMERS MU SCI 2 2018 9 The IODINE VALUE (or IODINE ADSORPTION Value or IODINE NUMBER or IODINE INDEX) in chemistry is the mass of iodine in grams that is consumed by 100 grams of a chemical substance. Iodine numbers are often used to determine the amount of unsaturation in fatty acids. This unsaturation is in the form of double bonds, which react with iodine compounds. The higher the iodine number, the more C=C bonds are present in the fat. It can be seen from the table that coconut oil is very saturated, which means it is good for making soap. On the other hand, linseed oil is highly unsaturated, which makes it a drying oil, well suited for making oil paints. In a typical procedure, the fatty acid is treated with an excess of the Hanuš or Wijs solution, which are, respectively, solutions of iodine monobromide (IBr) and iodine monochloride (ICl) in glacial acetic acid. Unreacted iodine monobromide (or monochloride) is then allowed to react with potassium iodide, converting it to iodine, whose concentration can be determined by titration with sodium thiosulfate The FATY ACIDS OF OUR INTEREST A WHY THEY ARE SO FOR US? January 2018/2 NATURAL POLYMERS MU SCI 2 2018 10 The common FATY ACIDS which are contained in the Vegetable Oils FATY ACID’S name Carbon Atoms Number Double Bonds Number Formulae Iodine Value Lauric 12 --- CH3(CH2)10COOH --- Myristic 14 --- CH3(CH2)12COOH --- Palmitic 16 --- CH3(CH2)14COOH --- Steraic 18 --- CH3(CH2)16COOH --- Oleic 18 1 CH3(CH2)7CH=CH-(CH2)7COOH 90 Linolic 18 2 CH3(CH2)4CH=CH-CH2-CH=CH (CH2)7COOH 181 Linolenic 18 3 CH3CH2CH=CH-CH2-CH=CH-CH2-CH=CH (CH2)7COOH 274 The FATY ACIDS - Sources and a Manufacturing Technology •Vegetable Oily Seeds •TECHNOLOGY •COLD PRESSING (Analogue of the so called Virgin Olive Oil) •Hot PRESSING (Analogue of the so called Olive Oil for Cooking) •Hydrocarbon's hot Extraction (Analogue of the so called Olive Oil for Soap and Cosmetic) •WASTES, so called OIL CAKE > Animal's Feeding January 2018/2 NATURAL POLYMERS MU SCI 2 2018 11 January 2018/2 NATURAL POLYMERS MU SCI 2 2018 12 Boiled linseed Oil : modified (treated) Linseed Oil Boiled linseed Oil adjusted (mixed): it contains some other Oils also, not the Linseed Oil only CHEMICAL BASIS OF THE MODIFICATION (TREATMENT): The –OOH Groups are arisen on the double Bonds of the higher fatty Acids Impregnating Linseed Oil: diluted by the volatile organic Solvents to decrease the Viscosity and so increase the Infusion to the impregnated Material, usually the Wood January 2018/2 NATURAL POLYMERS MU SCI 2 2018 13 454.jpg Boiled linseed Oil MANUFACTURE AIR SICCATIVE Raw linseed Oil Steam-jacketed Kettle The FATY ACIDS OF OUR INTEREST AND THEIR COMPOSITIONS January 2018/2 NATURAL POLYMERS MU SCI 2 2018 14 These Oils are used for the Oil based Paints and they are so called DRYING OILS COMPOSITIONS OF THE TYPICAL VEGETABLE OILS ACID Linseed Oil (% w/w) Poppy/Poppy-seed Oil (% w/w) Walnut oil (% w/w) Palmitic 6 10 8 Stearic 4 2 3 Oleic 22 11 15 Linolic 15 76 61 Linolenic 52 --- 12 OTHER 1 1 1 Ratio of the Palmitic to Stearic Acids 1,5 5,0 2,6 What is that of „OIL DRYING“ •IT IS NOT REAL DRYING (Evaporation of the Solvent)! •It is in Reality a Multistage Radical initiated Reaction, where the Group –OOH (Hydroperoxide) is arisen at first (Mass is increasing) , which then can initiate by its Decomposition a Crosslinking of the unsaturated Compounds (Fatty Acids in the Glycerides) and so the Mass is decreasing again January 2018/2 NATURAL POLYMERS MU SCI 2 2018 15 img483.jpg D G is here D of the Mass, not the Gibbs free Energy Change (D)! What is that of „OIL DRYING“ Better said, it is Solidification January 2018/2 NATURAL POLYMERS MU SCI 2 2018 16 img484.jpg Schematic showing of the OXIDATION and DEGRADATION of the Linseed Oil Film O=O …Oxygen, -OOH … Hydroperoxide, -OH … Alcoholic Group, -COOH … Carboxylic Group How to accelerate „OIL DRYING“? January 2018/2 NATURAL POLYMERS MU SCI 2 2018 17 Transition Valence Metals, e.g. Fe3+ , Co2+ , Mn2+ , Pb+2 So called SICCATIVE M(n+1)+ + R-OOH Mn+ + R-OO. + H+ The Metal in the lower Oxidation State react with the Hydroperoxide decomposing it and increasing its Oxidation State back up. The Cycle is closed so. Mn+ + R-OOH M(n+1)+ + R-O. + HO- Data from a Literature January 2018/2 NATURAL POLYMERS MU SCI 2 2018 18 img486.jpg img487.jpg Ferric Red are the Iron oxides with the Red-brown Colour Shades www.precheza.cz Ferric Pigments FEPREN D G is here D of the Mass, not the Gibbs free Energy Change (D)! DG as the Function of the Aging time t at 20 °C: 1.Linseed Oil without any Pigments 2.Linseed Oil with the ZnSO4 Pigment 3.Linseed Oil with the Cobalt Blue Pigment 4.Linseed Oil with the English Red Pigment 5. Time necessary to reach the Maximum on the „OIL DRYING“ Curve as the Function of the Ferric Red Pigment of the various Grades: 1.English Red 2.Caput Mortuum 3.Puzuola 4.Ferric Red Lefrane 5.Bayferox 6.Windsor Newton How to DECELERATE „OIL DRYING“ and alternatively Protect the „Dry“ Film against undesirable Degradation? •UV Stabilisers – against the Light Degradation –HALS, –UV Absorbers, –Excited States Scavengers –……….. •Inhibitors of the Radical Reactions acting against the „OIL DRYING“? January 2018/2 NATURAL POLYMERS MU SCI 2 2018 19 Natural RESINS January 2018/2 NATURAL POLYMERS MU SCI 2 2018 20 •They are gained by Bleeding (Resin Tapping) from the Tree Injury or the purposely done Cuts of the Tree’s, mainly the Fir Trees (e.g. Pine Tree) •They are MIXTURES of the mainly Terpenoid’s Compounds (the only Exception is SHELACK) and Essential/Ethereal Oils •They are the Viscous Liquids, called also as BALSAMS or DISCHARGES (THIS MIXTURES) •These BALSAMS are divided to RESINS & Essential/Ethereal Oils by Distillation to the SOLID MATERIAL (SOLIDS) & LIQUIDS • Natural RESINS January 2018/2 NATURAL POLYMERS MU SCI 2 2018 21 •BALSAM (DISCHARGE) • • •Terpenoid •(SOLID •MATERIAL) • Essential/Ethereal Oils (LIQUID) Bleeding (Resin Tapping) Natural RESINS versus Essential/Ethereal Oils January 2018/2 NATURAL POLYMERS MU SCI 2 2018 22 •Natural RESINS are the oligomeric, viscous, low Volatile Materials (Mixture of the Compounds) •Essential/Ethereal Oils are the Volatile, even at low Temperature. They are Water insoluble, oily Substances of their Mixtures, frequently aromatic and having the acrid/pungent Taste. •They are TERPENOIDE in both cases • Shellac January 2018/2 NATURAL POLYMERS MU SCI 2 2018 23 •Shellac is NOT the Vegetable Product! •Shellac is the Animal Product, Insect’s Secrete •Shellac doesn't contain Terpenoide Acids, but the Polyhydroxy Acids, mainly (up to 50 % w/w) of the Aleuritic Acid and its Oligomers •HOCH2(CH2)5CH(OH)CH(OH)(CH2)7COOH •Shellac is highly polar Substance > Solubility in the EtOH and in the other Alcohols and Glycols •Shellac is Water insoluble, but it is soluble in the alkali Solutions > the Binder for the China Ink Shellac – various Grades January 2018/2 NATURAL POLYMERS MU SCI 2 2018 24 Shellac - Use January 2018/2 NATURAL POLYMERS MU SCI 2 2018 25 •HISTORICAL USE •GRAMOPHONE RECORDS, even before the Use of the PVC Copolymers! •IT WAS FILLED BY THE VERY FINE GROUND SLATE! •CURRENT USE •Manufacture of the musical Instrument – the by Hand Varnishing of the Violin and also for some by Hand Vvarnishing of the woodwind Instruments made of the light Wood. •Surface Treatment of Wood by Shellac Polish at Restoration Work, what give the Wood excellent Gloss. •Furnace polishing (in the 18.–19. Centuries). •Food Additive E904, e.g. Impregnation of the Fruit and Vegetable Surface to keep the Freshness. ISOPRENE – basic Unit of the TERPENOIDS January 2018/2 NATURAL POLYMERS MU SCI 2 2018 26 Vzorec Systematic Name 2-methyl-buta-1,3-dien Other names 2-methyl-1,3-butadien Summary Formula C5H8 TERPENOIDS – the main Components of the NATURAL RESIN DENOMINATION CARBON ATOMS NUMBER State of Matter at normal Temperature (23 °C) MONOTERPENOID 10 Liquid SESQUITERPENOID 15 Liquid DITERPENOID 20 Solid State TRITERPENOID 30 Solid State January 2018/2 NATURAL POLYMERS MU SCI 2 2018 27 MONOTERPENE LIMOLENE (in the Orange Peel) SESQUITERPENE d KADILENE January 2018/2 NATURAL POLYMERS MU SCI 2 2018 28 DITERPENE Abietic Acid The most important natural Resins January 2018/2 NATURAL POLYMERS MU SCI 2 2018 29 Physical and Chemical Properties of the natural Resins Resin Acid Number (mg KOH/g) Saponification Number (mg KOH/g) Iodine Value (% I2/g) Softening Temperature (°C) Colophone 140 – 180 147 – 195 200 - 225 73 – 79 Venice Turpentine 75 - 95 105 - 120 120 - 145 136 – 138 Sandarac 130 - 150 180 - 200 70 - 100 110 - 120 Copal Mannila 130 - 150 180 - 200 70 - 100 110 - 120 Damara 25 - 40 35 - 40 55 - 65 84 – 86 Mastix 60 - 65 85 - 100 70 - 85 73 – 74 Shellac 40 - 60 200 - 250 4 - 10 82 - 88 Natural Resins – an Example January 2018/2 NATURAL POLYMERS MU SCI 2 2018 30 •Fir Trees > PINE •> Turpentine BALSAM (DISCHARGE) •> DESTILATION of the Essential/Ethereal Oils > Turpentine > Thinner (Diluent ) of the Boiled linseed Oil and Oil’s based Paint •> The Rest after DESTILATION (Bottoms) is the RESIN = COLOPHONE • COLOPHONE January 2018/2 NATURAL POLYMERS MU SCI 2 2018 31 •Hard and Brittle at Room Temperature •It is changing Hard to Soft at approx. 70 °C •It melts at approx. 120 °C •It is soluble in the Alcohols, Esters, Aromatics, Chlorine substituted Solvents, Ketones, Turpentine etc. •It contains mostly Abietic acid > its Oxidation results as the Brittleness, Reduction of the Solubility etc. •It is soluble in the Alkali > RESIN’S SOAPS •Co+2 Salts > SICCATIVE •Cu+2 Salts > Pigment & SICCATIVE •Hot Melts •Soldering > it destroys the Oxide’s Layers • • • COLOPHONE (eng. Rosin or Colophony or Greek Pitch, Yellow Rosin) January 2018/2 NATURAL POLYMERS MU SCI 2 2018 32 •Colophony or Greek Pitch > it is derived fro the Old Greek Town Colophon, fames for the export of the COLOPHONE •Other uses: –Surface Treatment of the Violin Bow to increase the Friction with the Strings –If mixed with some Waxes is used for Iron on the old paintings to the new under laid Canvas (Textile) > RENTOALAGE –Pharmacy –Food Industry –............. COLOPHONE (eng. Rosin or Colophony or Greek Pitch) January 2018/2 NATURAL POLYMERS MU SCI 2 2018 33 Essential/Ethereal Oils Example - Turpentine January 2018/2 NATURAL POLYMERS MU SCI 2 2018 34 The main Components are PINENE (a, b) • Solvent for the Oils based Paints • As the Mixture with the Beeswax or the Carnauba Wax is used as the Furnace Polishing Agent • Synthesis of the fragrant Substances, e.g. Camphor Venic (Venetian) Turpentine January 2018/2 NATURAL POLYMERS MU SCI 2 2018 35 Add to oil paints, mediums and varnishes for an exquisite jewel-like quality and tough, enamel-like surface. Derived from European larch trees, this resin has the CONSISTENCY OF HONEY and is offered in its pure, undiluted state. Dilute with 20% turpentine and use sparingly to a 5% maximum of the total paint mixture. Venic (Venetian) Turpentine January 2018/2 NATURAL POLYMERS MU SCI 2 2018 36 > European Larch Some Remarks more 1.The Trivial Names are most common in the Chemistry of the Natural Substances, frequently related to the place of the Occurrence of the Substance in Question 2.There are also the other Substances besides the main Natural Substances (Polymers) in the common Natural Substances Samples (Materials) 3.The Composition and the Amount of the accompanying Substances are related to the Substance’s Source and Place of the Origin, the harvesting Season etc. January 2018/2 NATURAL POLYMERS MU SCI 2 2018 37 Let’s go to the other RESINS and BALSAMS (DISCHARGES) January 2018/2 NATURAL POLYMERS MU SCI 2 2018 38 •DITERPENOIDE RESINS Let’s go to the other Resins & Balsams (DISCHARGES)! January 2018/2 NATURAL POLYMERS MU SCI 2 2018 39 •Canada Balsam (Balsam of Fir) •It is taken from the Canadian Fir •It is used for the Assembling of the Optical Devices, because having very suitable refractive Index, very close to that of the optical Glass •Venic (Venetian) Balsam •It is taken from the European Larch •It forms the Glossy not yellowing Film •It was used in Painting (Oil Painting) in the time of Rubens already, mixed with the Nuts Oil and Mastix • • Copal January 2018/2 NATURAL POLYMERS MU SCI 2 2018 40 January 2018/2 NATURAL POLYMERS MU SCI 2 2018 41 Copal is a name given to tree resin, particularly the aromatic resins from the copal tree Protium copal (Burseraceae) used by the cultures of pre-Columbian Mesoamerica as ceremonially burned incense and for other purposes. More generally, the term copal describes resinous substances in an intermediate stage of polymerization and hardening between "gummier" resins and amber. Copal is highly soluble in the EtOH and is (was) valuable ingredient in making a good wood varnish. It became widely used in the manufacture of furniture and carriages. COPAL versus Novolacs Novolacs = Synthetic Condensate of Phenol + Formaldehyde January 2018/2 NATURAL POLYMERS MU SCI 2 2018 42 •NOVOLACS are good soluble in the EtOH, •NOVOLACS resulting in the glossy and hard Paints (Coatings), •NOVOLACS can be used as the COPAL in the alcohol Varnishes, which were formerly called (in a simple Slang) only as „COPALS“, •NOVOLACS were sometimes used for the falsification of the genuine COPAL in the alcohol Varnishes Sandarac January 2018/2 NATURAL POLYMERS MU SCI 2 2018 43 It is taken from the Coniferous Tree which is growing in the Nord Africa It is used for the protective Coating on the Pictures and Antiquities It is the Components of the Oil Varnishes, being soluble in the: • Turpentine, • Aromatics, • Amyl alcohol. Let’s go to the other RESINS and BALSAMS (DISCHARGES) January 2018/2 NATURAL POLYMERS MU SCI 2 2018 44 •TRITERPENOIDE RESINS Mastic (Mastix) January 2018/2 NATURAL POLYMERS MU SCI 2 2018 45 Mastic (Mastix) is the Resin, which is taken from the little Bush MASTIC TREE (Pistacia lentiscus) growing on the Greek Island Chios. January 2018/2 NATURAL POLYMERS MU SCI 2 2018 46 Mastic is used in some varnishes. Mastic varnish was used to protect and preserve photographic negatives. Mastic is also used in perfumes, cosmetics, soap, body oils, and body lotion. Chios Mastic is a known spice in the Eastern Mediterranean. It is commonly used for baking and cooking, adding its aroma to foodstuffs such as brioches, ice-cream and other desserts. It is especially known to the Arabian cuisine, but recently mastic is also increasingly used in Japanese cooking. One of the earliest uses of Mastic was as chewing gum; hence, the name. Mastic-flavored chewing gum is sold in Syria, Lebanon, Turkey, and Greece. Mastic is used in ice cream, sauces, and seasoning in Lebanon. In Egypt, mastic is used in vegetable preserves, in jams that have a gummy consistency, in soups, and in the preparation of meats. In Morocco, mastic is used in the preparation of smoked foods. Mastic has been used as a medicine since antiquity and is still used in traditional folk medicine of the Middle East. Mastic contains antioxidants and also has antibacterial and antifungal properties. Mastic is the Components of the Oil Varnishes, being soluble in the: • Turpentine, • Aromatics, • Amyl alcohol. Dammar gum January 2018/2 NATURAL POLYMERS MU SCI 2 2018 47 • DAMMAR GUM has a low IODINE VALUE > low Tendency to Yellowing and Polymerization • Dammar gum as the Component of the Varnishes gives them high Gloss DAMMAR GUM is soluble in the: Turpentine, Alcohols, Ketones, Esters, … January 2018/2 NATURAL POLYMERS MU SCI 2 2018 48 DAMMAR GUM is used in foods, as a clouding or glazing agent, and in incense, varnish and other products. Dammar varnish, made from dammar gum mixed with turpentine, was introduced as a picture varnish in 1826; commonly used in oil painting, both during the painting process and after the painting is finished. Dammar crystals are also dissolved in molten paraffin wax to make batik, to prevent the wax from cracking when it is drawn onto silk or rayon. Dammar crystals are dissolved into beeswax with pigment added to harden it in order to make encaustic paints. Dammar resins were often used in the past to caulk ships, frequently together with pitch or bitumen. DAMMAR, also called DAMMAR GUM, or DAMAR GUM, is a resin obtained from the trees in India and East Asia. Most is produced by TAPPING TREES, however, some is collected in fossilised form from the ground. The gum varies in colour from clear to pale yellow, while the fossilised form is grey-brown. DAMMAR GUM is a triterpenoid resin, containing a large number of triterpenes and their oxidation products. Many of them are low molecular weight compounds (dammarane, dammarenolic acid, oleanane, oleanonic acid, etc.), but dammar also contains a polymeric fraction, composed of polycadinene.