1 Biobased thermosets Biobased thermoplastic polymers (such as polylactic acid) are commercially available, but have minor importance in composites, so they are not discussed here MSK

2 Biobased polymers: two strategies 1.Polymers formed in biomass during life cycles of green plants, animals, bacteria and fungi Natural polymers: proteins, chitin, polyesters produced by bacteria, lignin, carbohydrates … Extraction, processing, reactive modification is needed to obtain a thermoset 2.Chemicals extracted from biomass Vegetable oils, lactic acid, bioethanol,…. Many sources: grown crops, by- products and waste from pulp and paper, food production, municipal waste streams,… Thermoset polymers can be synthesised, with varying biomass content Silk Bacterial PHB Lactic acid from corn MSK

3 Biothermosets are possible to make from: Carbohydrates: sugars, starch, cellulose Lignin Vegetable oils: linseed oil, soy oil, olive oil, corn oil, palm oil MSK

4 Lignin structure MSK

TransFurans Chemicals BioRez furanic resins Furfural is obtained by hydrolysis of hemicellulose 10 wt-% of a plant carbohydrate content can be converted to furfural Annual production tonnes 2004 (Wikipedia) Furfural and furfuryl alcohol can be reacted with phenols to a thermoset Processing and properties like phenolic resins 5MSK

Polylactide oligomer thermoset Branched lactic acid oligomer terminated with methacrylic groups Free radical polymerisations with or without reactive solvents Developed by JVS Polymers (Jukka Seppälä) POLLIT, LAIT-X products Core molecule C=C group Lactide branch J Appl Polym Sci 86 (2002) MSK

Polylactide thermoset synthesis 1.Formation of lactide arm 2.Formation of branched structure 3.Functionalisation to get reactive 4.Crosslinking by free radical polymerisation 7MSK

Office chair demonstrator Natural fibres Non-wovens; cellulose, wool, flax Woven fabrics; flax, jute, hemp Thermosets POLLIT resin Cognis Tribest Processing Prepreg Compression moulding 8MSK

9 Vegetable oils One of the oldest chemical raw materials still used by humans in technical applications Plant oil annual consumption around 100 million tonnes in 2000 Reactive double bonds in some oils: Linseed oil: an old binder in paints Linoleum carpet 1860 Curing by oxidative drying Chemical modification (epoxidation) increases reactivity MSK

10 Plant oils are triglycerides MSK

Fatty acids Linear saturated or unsaturated acids Stearic acid - a C18 saturated fatty acid Linoelic acid – a C18 unsaturated fatty acid MSK

12 Plant oil composition is varying in different plants: Typically 14 to 22 carbons in length and 0 to 3 unsaturated double bonds per fatty arm MSK

13 Ref: Chemtech 1999 Epoxidation of soy-oil MSK

A triglyceride is a ester of glycerol and fatty acids Fatty acid Glycerol Esterbond MSK

15 Reactive sites in the triglyceride can be functionalized into a cross-linking site The double bonds The allylic carbons The ester groups MSK

University of Borås development: Resins based on soybean oil Methacrylic anhydride modified soybean oil Methacrylated soybean oil Acetic anhydride modified soybean oil Methacrylate group Acetate group 16MSK

17 Henry Fords soybean car Description: Presented August 13, plastic panels 35 % weight saving compared to steel cars at that time Soybean resin, hemp, flax, ramie or soy bean fiber, phenolic resin Motivation: Utilise agricultural products in industrial products Safer car with plastic panels due to toughness Shortage of metals Source: MSK

Green racing car concept from University of Warwick, UK 18MSK

Ashland ENVIREZ® resins Soy bean oil based thermoset, ethanol containing Peroxide curing Developed for John Deere farming machines Biobased content: 12 wt-% -to 21 wt-%, will be increased Can be processed by all common methods; lamination, infusion, SMC/BMC, casting, pultrusion Available in Europe and US Campion Marine, Canada 19MSK

20MSK

Glycerin is a potential chemical feed- stock MSK

AMROY EUROPE OY EpoBiox Biobased epoxyresin Phenols from pulp processing are converted to Bisphenol A (not food biomass!) Epichlorhydrine made from plant oil glycerol 50 to 90 wt-% biobased content Different viscosity grades available 4000 tonnes production capacity in Finland 22MSK

DSM Palapreg ECO P An vinyl ester resin (?) 55 % of the raw material from bio sources SMC and BMC applications (automotive) Low shrink, equal mechanical performance compared to oil based resins in the application 23MSK

ASTM D6866: BIOBASED CONTENT IN A MATERIAL Biobased content: the fraction biobased carbon ( 14 C) of the total organic carbon content In atmosphere the CO 2 carbon is both isotopes 12 C and 14 C Half life of 14 C is 5730 years Fossil feed stock will not contain any 14 C isotope MSK

25 Challenges for biomass based composites RAW MATERIAL SOURCE -Fibre - Bioresin PRODUCTION -Fibre production - Bioresin production -Composite production -End product production PROPERTIES & PERFORMANCE -Fibre - Bioresin -Composite -End product MARKETING & SALE -Product performance -Customer expectations -Govermental directives -Public opinion MSK

26 BIOMASS Produced by photosynthesis Very large annual production Clean, effecient, high capacity, complex chemicals INDUSTRIAL USE -Pulp&paper -Textiles -Building material -Natural chemicals & Resins -Fuel RECREATIONAL USE -Tourism -National parks ECOLOGICAL USE -Preservation of ecosystems and wild life -Needed for keeping climate balance FOOD -Agricultural -Animal production -Fish production -Wild animal hunting MSK

27 Genetic modification? For tailoring plants to produce industrially usable raw materials Ex: starch from potatoes, regulation of oil types in oil plants Consumer concerns and green movement are critical MSK

28 Necessary developments: Fibre processing techniques into technical reinforcements Dust and microorganism in plants can be health hazards Hydrophilicity of natural fibers causes water sensitivity (rotting and swelling) Matrix incompatibility causes poor mechanical properties Seasonal variability in plant properties Better understanding about mechanical properties and structure Temperature stability (processability and recycling MSK

29 Biobased composites - questions: A chemical processing is often necessary Plant genetic modification can be necessary Environmental effect must be evaluated by life cycle analysis Should the agricultural area be used for food or raw material production? Today's highly effective agriculture affects the environment MSK