research areas
DESCRIPTION
Dr. Andrew Clark Senior Lecturer in Synthetic Chemistry. Research areas. Natural product isolation and total synthesis. Chemistry and biology of free radicals. Development of synthetic methodology using copper, iron and ruthenium. Functional Genomics / Chemical Genetics / Interactomics. - PowerPoint PPT PresentationTRANSCRIPT
Research areas
Natural product isolation and total synthesis.
Chemistry and biology of free radicals
Dr. Andrew ClarkSenior Lecturer in Synthetic Chemistry
Development of synthetic methodology using copper, iron and rutheniumFunctional Genomics / Chemical Genetics / InteractomicsUse of plants in renewable plastics manufacture
Use of plants in renewable plastics manufacturePOLYMERS and COMPOSITES
Resins/MonomersNormally made from organic chemicals which are petrochemicalin origin.
StrengthenersNormally a fibre incorporated into the polymer to increase mechanical strength.
FillersCheap 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
0
500
1000
1500
2000
2500
Ar amid Car bon Flax E -glass Hemp
: Specific tensile strengths of synthetic and natural fibres
hydroxylatedmonomers
OH
OH
POLYURETHANESFlexible and rigid foamselastomers and extrusions,coatings, adhesives
10 6 tonnes per annum
POLYESTERSFlooring, autobody repair, boat hulls
Epoxidisedmonomers
O
O
EPOXY RESINSProtective coatings, adhesivesflooring, plasticizers, foams
COMMON MONOMER FEEDSTOCKS
hydroxylatedmonomers
POLYURETHANES
OH
OH
Isocyanatemonomers
NCO
NCO
catalyst
hydroxylatedmonomers
O
OO
HN
Isocyanatemonomers
Renewable sources of monomers for polyurethane synthesis
hydroxylatedmonomers
OH
OH
OH
OH
C15H29
TYPE 1CASTOR OIL
OOO
OR
OR
COR
TYPE 2CARDANOL
cashew nut shell liquidOH
C15H29NN
OH
steps
OOO
OR
OR
OR
oleic
linoleic
linolenic
Rapeseed
H2O2, W, H3PO4Room temperature
epoxideO
alcoholOHOH
acid, H2O
VernolicO
OOO
OR
OR
OR
Euphorbia
acid, H2O
OHOH
RAPESEED
O
O
epoxidationRAPESEED
HO
HO
OH
OH
RASOR
ring openingRAPESEED
O
O
EUPHORBIA
HO
HO
OH
OH
low-EURE
ring openingRAPESEEDEUPHORBIA
OH
OH
OH
OH
OHOH
OHOH
high-EURE
epoxidation
ring openingRAPESEEDEUPHORBIA
INFRA RED OF RAPESEED AND HYDROXYLATED RAPESEED
RAPESEED
O
O
epoxidationRAPESEED
HO
HO
OH
OH
RASOR
ring openingRAPESEED
OO
O
O
RAPESEED
O
OH
HO
RAPESEED
HOOH
HOOH
OH
OH
HO
RAPESEED
HOOH
HOO
OH
OH
OH
HO
RAPESEED
HO
HO
+
OH
OH
O
O
EUPHORBIA
HO
HO
OH
OH
low-EURE
ring openingRAPESEEDEUPHORBIA
OH
OH
OH
OH
OHOH
OHOH
high-EURE
epoxidation
ring openingRAPESEEDEUPHORBIA
4000 3500 3000 2500 2000 1500 10000
20
40
60
80
100
C=O
OH
Euphorbia low-OH Euphorbia high-OH
Tran
smitt
ance
(%)
Wavenumber (cm-1)
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-ISOCYANATESMDITDI
COMPOSITES HEMP (H)
MISCANTHUSFLAX
JUTE (J)
COMPRESSION MOULDING
4000 3500 3000 2500 2000 1500 10000
20
40
60
80
100
C=O
OH and NH
NCO
Euphorbia-OH Euphorbia 50min Rapeseed 50min
Tran
smitt
ance
(%)
Wavenumber (cm-1)
IR spectra of 50 min cured rapeseed and euphorbia oil
0 10 20 30 40 50 60 70 80 900
20
40
60
80
100
120
140
160
180
200
Isothermal cure characteristics of MDI polymerised
rapeseed resin (50oC, 180 J/g)
RASOR
Hea
t of r
eact
ion
(del
ta H
-J/g
)
Time (min)
Differential scanning calorimetry (DSC) analysis:
0 200 400 600 8000
20
40
60
80
100 Rapeseed oil Hydroxylated oil MDI polymerised Hemp-RASOR
composite
Mas
s los
s (%
)
Temperature (oC)
THERMAL GRAVIMETRIC ANALYSIS OF MATERIALS
RAPESEED
The loss in mass as a function of temperature
0 200 400 600 8000
20
40
60
80
100 Rapeseed oil Hydroxylated oil MDI polymerised Hemp-RASOR
composite
Mas
s los
s (%
)
Temperature (oC)
0 200 400 600 8000
20
40
60
80
100 Euphorbia oil Hydroxylated Euphorbia resin Hemp-EURE
composite
Mas
s los
s (%
)
Temperature (oC)
THERMAL GRAVIMETRIC ANALYSIS OF MATERIALS
RAPESEED EUPHORBIA
The loss in mass as a function of temperature
0 200 400 600 800 10000
5
10
15
20
25
30 Neat EURE Hemp-EURE
Mas
s los
s (%
)
Degradation temperature (oC)
THERMAL GRAVIMETRIC ANALYSIS OF MATERIALS
EUPHORBIA
0 1 2 3 4 50
5
10
15
20
25
30
35
40
45
HEURE low-OH HEURE high-OH Alk HEURE high-OH
Tens
ile st
reng
th (M
Pa)
Strain (%)
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.50
10
20
30
40 Untreated HRASOR Alk HRASOR
Tens
ile st
reng
th (M
Pa)
Strain (%)
Untreated and alkali treated hemp-EURE and hemp-RASOR composites
Compositetype
Fibre volume(%)
Tensile strength(MPa)
Young’s Modulus(GPa)
Composite density(Kg/m3)
Impact strength(kJ/m2)
ILSS(MPa)
HEURE-low-OH
21.05 22.91 (1.06)
2.31 649.55 18.81(2.17)
3.12
HEURE-high-OH
18.89 26.56 (1.85)
2.78 625.07 7.03(1.13)
3.49(0.45)
HRASOR 19.92 38.84 (2.21)
3.40 697.09 9.25(1.21)
3.88(0.45)
AHEURE-high-OH
20.39 34.69(3.76)
3.13 675.46 9.15(1.64)
4.73(0.76)
AHRASOR 19.20 23.82(2.96)
2.35 633.16 10.47(2.01)
3.81(0.43)
JEURE-high-OH
23.77 55.52(2.60)
4.26 658.59 10.60(2.27)
4.95(0.43)
JRASOR 23.74 46.38(3.37)
3.89 704.93 13.70(1.95)
3.99(0.82)
AJEURE-high-OH
22.69 26.76(2.23)
2.52 663.34 8.33(0.88)
3.45(0.45)
AJRASOR 22.70 26.84(1.60)
2.61 655.23 13.34(1.78)
3.55(0.66)
1 2 3 40
10
20
30
40
50
60
AJRASORJRASORAJEUREhigh-OH
JEUREhigh-OH
Tens
ile st
reng
th (M
Pa)
0
2
4
6
8
10
12
14
16
18
20
22
ALkhemp-RASOR
UnhempRASOR
Alkhemp-EUREhigh-OH
Unhemp-EUREhigh-OH
Unhemp-EURElow-OH
Impa
ct st
reng
th (k
J/m
2 )
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.
Cost of oil production per kiloEuphorbia lagascae £1.61Rapeseed oil £2.11Castor oil £1.21 * not including import costs
Cost of complete polyurethane production per kiloEuphorbia lagascae £1.54Rapeseed oil £1.88Petrochemical £2.50-£9.50
Energy required in monomer production 1.9kg of fossil fuel per kg of monomerEquates to 3.1 kg of CO2 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 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, 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. Weightman ADAS Consultancy Ltd, Battlegate Road, Boxworth, Cambs, CB3 8NN
ACKNOWLEDGEMENTS