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