Research areas Natural product isolation and total synthesis. Chemistry and biology of free radicals Dr. Andrew Clark Senior Lecturer in Synthetic Chemistry Development of synthetic methodology using copper, iron and ruthenium Functional Genomics / Chemical Genetics / Interactomics Use of plants in renewable plastics manufacture

POLYMERS and COMPOSITES Resins/Monomers Normally made from organic chemicals which are petrochemical in origin. Strengtheners Normally a fibre incorporated into the polymer to increase mechanical strength. Fillers Cheap organic or inorganic materials used to bulk the polymers and to alter physical properties Plant oils e.g. rape oil, linseed oil, sunflower oil, soya oil Plant fibres e.g. hemp, flax, jute, miscanthus Plant protein / waste e.g. rape meal

ADVANTAGES OF PLANT PRODUCTS OVER PETROCHEMICALS Non-toxic, Biodegradable, Non-polluting in water courses, Sustainable, Recyclable? Besides a competitive price, the chemical industry also wants improved or new properties from end products derived from vegetable oils

Vegetable Oils as Polymer Feedstocks (monomers) Rapeseed oil Euphorbia oil Jute Hemp Plant fibres for composites

: Specific tensile strengths of synthetic and natural fibres

COMMON MONOMER FEEDSTOCKS

Renewable sources of monomers for polyurethane synthesis TYPE 1 CASTOR OIL TYPE 2 CARDANOL cashew nut shell liquid

INFRA RED OF RAPESEED AND HYDROXYLATED RAPESEED

Infra Red of modified low hydroxylated and high hydroxylated euphorbia

POLYMERISATION THREE CLASSES of RESIN RAPESEED HYDROXYLATED RESIN (RASOR) EUPHORBIA HIGH HYDROXYLATED RESIN (high-EURE) EUPHORBIA LOW HYDROXYLATED RESIN (low-EURE) DI-ISOCYANATES MDI TDI COMPOSITES HEMP (H) MISCANTHUS FLAX JUTE (J) COMPRESSION MOULDING

IR spectra of 50 min cured rapeseed and euphorbia oil

Differential scanning calorimetry (DSC) analysis:

THERMAL GRAVIMETRIC ANALYSIS OF MATERIALS RAPESEED The loss in mass as a function of temperature

THERMAL GRAVIMETRIC ANALYSIS OF MATERIALS RAPESEEDEUPHORBIA The loss in mass as a function of temperature

THERMAL GRAVIMETRIC ANALYSIS OF MATERIALS EUPHORBIA

Untreated and alkali treated hemp-EURE and hemp-RASOR composites

Composite type Fibre volume (%) Tensile strength (MPa) Young’s Modulus (GPa) Composite density (Kg/m 3 ) Impact strength (kJ/m 2 ) ILSS (MPa) HEURE-low- OH (1.06) (2.17) 3.12 HEURE-high- OH (1.85) (1.13) 3.49 (0.45) HRASOR (2.21) (1.21) 3.88 (0.45) AHEURE-high- OH (3.76) (1.64) 4.73 (0.76) AHRASOR (2.96) (2.01) 3.81 (0.43) JEURE-high- OH (2.60) (2.27) 4.95 (0.43) JRASOR (3.37) (1.95) 3.99 (0.82) AJEURE-high- OH (2.23) (0.88) 3.45 (0.45) AJRASOR (1.60) (1.78) 3.55 (0.66)

SCANNING ELECTRON MICROSCOPY RAPESEED PU RAPESEED-HEMP COMPOSITE EUPHORBIA PU EUPHORBIA-HEMP COMPSITE

WEATHERABILITY NO evidence of major decomposition after 6 months simulated Solar UV radiation BIODEGRADABILITY Samples buried in bags 6 x 6 cm (pore size 20 micron) Bags recovered after three and six weeks Weight loss and colonising flora analysis SampleWeight loss after 6 weeks [%] Euphorbia polyurethane (EURE)15.2 Rapeseed polyurethane/hemp composite (hemp-RASOR) 52.2 Euphorbia polyurethane/hemp composite (hemp-EURE) 50.3 Rapeseed polyurethane (EURE)12.4

= ladder DNA, 2-5 = soil DNA, 6-9 = 3 wks, = 6 wks 6, 10 = microflora DNA from EURE 7, 11 = microflora DNA from hemp-RASOR 8, 12 = microflora DNA fromhemp-EURE 9, 13 = microflora DNA from RASOR BIODEGRADABILITY RASOR SEM 1= 3 weeks hemp-EURE 2= 3 weeks hemp-RASOR 3= 6 weeks hemp-EURE 4= 6 weeks hemp-RASOR

Economics. Cost of oil production per kilo Euphorbia lagascae £1.61 Rapeseed oil£2.11 Castor oil£1.21 * not including import costs Cost of complete polyurethane production per kilo Euphorbia lagascae £1.54 Rapeseed oil£1.88 Petrochemical£2.50-£9.50 Energy required in monomer production 1.9kg of fossil fuel per kg of monomer Equates to 3.1 kg of CO 2 emissions per Kg of monomer

A range of materials from rapeseed oil and euphorbia oil have been prepared and analysed. Properties of materials produced differ depending upon the type of oil used. Fibre composites of resins give superior properties to resins alone. Biodegradability may be controllable The increased range of materials available from this project will broaden the portfolio of potential industrial applications of materials from renewables which should lead to an increased value added market for fibres and oil crops in the UK agricultural sector. Euphorbia lagascae is a potential new crop for renewable materials production CONCLUSIONS AND RELEVANCE

Future work In depth biodegradation studies. Can we control rate of degradation? Use of other oilseed crops and fibre crops. Use of fillers (rapemeal) Portfolio of materials from renewables to showcase to industry

Chemistry Department, University of Warwick, Coventry, CV4 7AL Dr. A. J. Clark, Project leader, Chemistry, monomer production Dr. L. Mwaikambo, Polymer synthesis and characterisation Prof. T. J. Kemp,Weatherometry Mrs. A. Mohd Rus,Weatherometry Advanced Technology Centre, Warwick Manufacturing Group, University of Warwick, Coventry, CV4 7AL, Dr. N. J. Tucker,Project leader, Composites, mechanical testing Biological Sciences, University of Warwick, Coventry, CV4 7AL, Dr. M. Krsek,Biodegradability Prof. E. M. H. Wellington,Biodegradability ADAS (Euphorbia supplier) Mr. D. Turley,Formally of ADAS, High Mowthorpe, Duggleby, Malton, N Yorks, YO17 8BP. Dr. R. M. WeightmanADAS Consultancy Ltd, Battlegate Road, Boxworth, Cambs, CB3 8NN ACKNOWLEDGEMENTS