Vegetable Oils as Polymer Feedstocks
NF0513
Rapeseed oil
Euphorbia 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)
HYDROXYLATED MONOMERS
POLY(URETHANES)
O
HO
catalyst
OH
OCN
O
O
NCO
N
H
Renewable sources of monomers for poly(urethane) synthesis
2) Cardanol (Cashew Nut Shell Liquid)
1) Castor oil
O
O
R
O COR
O
R
O
OH
EWABLE RESOURCES AS CHEMICAL FEEDSTOCKS
OH
OH
steps
C15H29
N
N
OH
C15H29
oleic
O
O
R
O
O
R
O
R
O
O
O
R
O
O
R
O
R
O
linoleic
linolenic
O
Vernolic
Rapeseed
Euphorbia
H2O2, W, H 3PO4
Room temperature
acid, H 2O
OH
OH
O
epoxide
acid, H 2O
HO
OH OH
alcohol
OH OHOH
POLYMERISATION
THREE CLASSES of RESIN
RAPESEED HYDROXYLATED RESIN (RASOR)
EUPHORBIA HIGH HYDROXYLATED RESIN (EURE)
EUPHORBIA LOW HYDROXYLATED RESIN (low-EURE)
DI-ISOCYANATES
MDI
TDI
COMPOSITES
HEMP
MISCANTHUS
FLAX
COMPRESSION MOULDING
Feedstock analysis
1H 400MHz Nuclear Magnetic Resonance
13C 100 MHz Nuclear Magnetic Resonance
Fourier Transform Infra Red Spectroscopy
Matrix Assisted Laser Desorption Ionisation-Time Of Flight Mass Spectrometry
Electrospray Fourier Transform Ion Cyclotron Resonance Mass Spectrometry
Elemental analysis
Gel Permeation Chromatography
Polymer Analysis
Differential Scanning Calorimetry
Thermal Gravimetric Analysis
Scanning Electron Microscopy
Property Analysis
Instron Tensile testing machine
Weatherometer
Biodegradability studies
THERMAL GRAVIMETRIC ANALYSIS OF MATERIALS
RAPESEED
Rapeseed oil
Hydroxylated oil
MDI polymerised
Hemp-RASOR
composite
100
100
Euphorbia oil
Hydroxylated
Euphorbia resin
Hemp-EURE
composite
80
Mass loss (%)
80
Mass loss (%)
EUPHORBIA
60
40
20
60
40
20
0
0
200
600
400
800
0
0
200
400
600
o
Temperature ( C)
o
Temperature ( C)
800
THERMAL GRAVIMETRIC ANALYSIS OF MATERIALS
RAPESEED
EUPHORBIA
30
RASOR
Hemp-RASOR composite
30
Neat EURE
Hemp-EURE
25
25
Mass loss (%)
Mass loss (%)
20
15
10
20
15
10
5
5
0
0
100
200
300
400
500
600
Temperature (%)
700
800
900
1000
0
200
400
600
800
o
Degradation temperature ( C)
1000
STRESS-STRAIN CURVES
40
35
35
RAPESEED
30
EUPHORBIA
30
Stress (MPa)
Stress (MPa)
25
20
15
25
20
15
10
10
5
5
0
0
0
1
2
3
4
5
6
7
8
0
1
2
5
6
Stress-strain curve of hemp-euphorbia composite
Stress-strain curve of hemp-rapeseed composite
Tensile Strength
(MPa)
4
Strain (%)
Strain (%)
Composite type
3
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
7
SCANNING ELECTRON MICROSCOPY
RAPESEED PU
EUPHORBIA PU
RAPESEED-HEMP COMPOSITE
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
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
BIODEGRADABILITY
RASOR SEM
123 4 5 6 7 8 910111213
1= 3 weeks hemp-EURE
2= 3 weeks hemp-RASOR
3= 6 weeks hemp-EURE
4= 6 weeks hemp-RASOR
1 = ladder DNA, 2-5 = soil DNA,
6-9 = 3 wks, 10-13 = 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
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
CONCLUSIONS AND RELEVANCE
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.
ACKNOWLEDGEMENTS
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,
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,
Malton, N
Dr. R. M. Weightman
Formally of ADAS, High Mowthorpe, Duggleby,
Yorks, YO17 8BP.
ADAS Consultancy Ltd, Battlegate Road, Boxworth,
Cambs, CB3 8NN