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Vegetable Oils as Polymer FeedstocksNF0513
Rapeseed oil
AIMS: Evaluate and compare the potential of both rapeseed and Euphorbia oil as feedstocks for use in the polymer industry (including types of materials produced, their properties and their economics)
Euphorbia oil
RAPESEED OIL AS A CHEMICAL FEEDSTOCK
FEEDSTOCKS FOR THE POLYMER INDUSTRY
Hydroxylated monomers
Poly(urethanes)Flexible and rigid foams, elastomers, extrusions, coatings, adhesives.
Poly(esters), unsaturated poly(esters) Flooring, auto body repair, boat hulls
Epoxidised monomers Epoxy resins Protective coatings, adhesives, flooring, plasticizers, foams
HO OH
OCN NCO
O O N H
O
OOO
OR
COR
OR OH
HYDROXYLATED MONOMERS
C15H29
POLY(URETHANES)
OH
RENEWABLE RESOURCES AS CHEMICAL FEEDSTOCKS
C15H29
Renewable sources of monomers for poly(urethane) synthesis
N
1) Castor oil
N
OH
2) Cardanol (Cashew Nut Shell Liquid)
steps
catalyst
OH
OOO
OR
OR
OR
oleic
linoleic
linolenic
Rapeseed
H2O2, W, H3PO4Room temperature
epoxideO
alcoholOHOH
acid, H2O
Vernolic
O
OOO
OR
OR
OR
Euphorbia
acid, H2O
OHOH
OHOHHO OH
POLYMERISATION
THREE CLASSES of RESIN
RAPESEED HYDROXYLATED RESIN (RASOR)EUPHORBIA HIGH HYDROXYLATED RESIN (EURE) EUPHORBIA LOW HYDROXYLATED RESIN (low-EURE)
DI-ISOCYANATESMDITDI
COMPOSITES HEMP
MISCANTHUSFLAX
COMPRESSION MOULDING
Feedstock analysis1H 400MHz Nuclear Magnetic Resonance13C 100 MHz Nuclear Magnetic ResonanceFourier Transform Infra Red SpectroscopyMatrix Assisted Laser Desorption Ionisation-Time Of Flight Mass SpectrometryElectrospray Fourier Transform Ion Cyclotron Resonance Mass Spectrometry Elemental analysisGel Permeation Chromatography
Polymer AnalysisDifferential Scanning CalorimetryThermal Gravimetric AnalysisScanning Electron Microscopy
Property AnalysisInstron Tensile testing machineWeatherometerBiodegradability studies
0 200 400 600 8000
20
40
60
80
100 Rapeseed oil Hydroxylated oil MDI polymerised Hemp-RASOR
composite
Mas
s lo
ss (
%)
Temperature (oC)
0 200 400 600 8000
20
40
60
80
100 Euphorbia oil Hydroxylated Euphorbia resin Hemp-EURE
composite
Mas
s lo
ss (
%)
Temperature (oC)
THERMAL GRAVIMETRIC ANALYSIS OF MATERIALS
RAPESEED EUPHORBIA
100 200 300 400 500 600 700 800 900 10000
5
10
15
20
25
30
RASOR Hemp-RASOR composite
Mas
s lo
ss (
%)
Temperature (%)
0 200 400 600 800 10000
5
10
15
20
25
30 Neat EURE Hemp-EURE
Mas
s lo
ss (
%)
Degradation temperature (oC)
THERMAL GRAVIMETRIC ANALYSIS OF MATERIALS
RAPESEED EUPHORBIA
0
5
10
15
20
25
30
35
0 1 2 3 4 5 6 7 8
Stress-strain curve of hemp-rapeseed composite
Strain (%)
Stre
ss (
MPa
)
0 1 2 3 4 5 6 70
5
10
15
20
25
30
35
40
Stress-strain curve of hemp-euphorbia composite
Stre
ss (
MPa
)
Strain (%)
STRESS-STRAIN CURVES
RAPESEED EUPHORBIA
Composite type Tensile Strength(MPa)
Young’s Modulus(GPa)
Strain(%)
Charpy Impact(kJ/m2)
Hemp-rapeseed 30.89 0.78 7.38 10.27
Hemp-euphorbia 37.47 1.05 6.92 8.91
SCANNING ELECTRON MICROSCOPY
RAPESEED PU RAPESEED-HEMP COMPOSITE
EUPHORBIA PU EUPHORBIA-HEMP COMPSITE
WEATHERABILITYNO evidence of major decomposition after
6 months simulated Solar UV radiation
BIODEGRADABILITYSamples buried in bags 6 x 6 cm (pore size 20 micron)
Bags recovered after three and six weeksWeight loss and colonising flora analysis
Sample Weight 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
123 4 5 6 7 8 910111213
1 = ladder DNA, 2-5 = soil DNA, 6-9 = 3 wks, 10-13 = 6 wks
6, 10 = microflora DNA from EURE7, 11 = microflora DNA from hemp-RASOR8, 12 = microflora DNA fromhemp-EURE9, 13 = microflora DNA from RASOR
BIODEGRADABILITY
RASOR SEM
1= 3 weeks hemp-EURE2= 3 weeks hemp-RASOR3= 6 weeks hemp-EURE4= 6 weeks hemp-RASOR
1 2 3 4
Economics.Current work is about to focus upon comparing the economics / competitiveness / market opportunities of materials prepared from the above vegetable oils with those from commercial sources.
The outputs of this objective will be:
A full cost/benefit analysis for each of the oils in terms of procedure, time and consumables costs.
Quantification of the benefits of each approach in terms of environmental protection
Identification of an acceptable premium for the provision of renewable/biodegradable materials A list of potential users of the materials and a schedule for exploitation if appropriate.
Future work
Polymers from low hydroxylated euphorbia.
In depth biodegradation studies. Can we control rate of degradation?
Use of other fibre crops.
Use of fillers (rapemeal)
Synthesis of biopolystyrene from vegetable oils
Blending of existing polymers with renewable polymers, properties, economics.
Portfolio of materials from renewables to showcase to industry
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, and is investigating economic ways of producing new chemical feedstocks and polymers from UK crops.
CONCLUSIONS AND RELEVANCE
Chemistry Department, University of Warwick, Coventry, CV4 7ALDr. A. J. Clark*, Project leader, Chemistry, monomer productionDr. L. Mwaikambo, Polymer synthesis and characterisationProf. T. J. Kemp, WeatherometryMrs. A. Mohd Rus, Weatherometry
Advanced Technology Centre, Warwick Manufacturing Group, University of Warwick, Coventry, CV4 7AL, Dr. N. J. Tucker, 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. Weightman ADAS Consultancy Ltd, Battlegate Road, Boxworth,
Cambs, CB3 8NN
ACKNOWLEDGEMENTS