Plant Based Resins for Fibre Composites - USQ ePrintseprints.usq.edu.au/3120/1/Presentation.pdf ·...
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Plant Based Resins for Fibre Composites
Dr. Pavel Faigl
Dr. David Rogers
Mr. Romain Maurin
Prof. Gerard van Erp
Centre of Excellence in Engineered Fibre Composites
University of Southern Queensland, Toowoomba, 4350
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Aims of vegetable oil resin work at CEEFC
• Explore options for sustainable production of several classes ofthermosetting resin
• Save resin costs while providing value-adding opportunities for Australian farmers
• Short term: Provide viable technology for immediate partial resin replacement:– 30% in structural applications– 50% in semi-structural applications
• Long term: Explore development of 100% sustainably sourced composites, combining wholly-vegetable oil resins with natural fibrereinforcements
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Vegetable Oil Resins – Background
• Cost. Resins used in highly-filled civil engineering composites constitute approx. 80% of total cost
• Price increases. Resin costs have increased steadily over the last 2-3 years in proportion to increase in crude oil price.
• Uncertainty of supply. Crude oil supplies are finite and unsustainable over the long term. Viable alternatives to crude oil based resins will need to be found to ensure the sustainability of thermosetting resin supply.
• “Green Factor”. Environmentally sustainable technologies increasingly command price premiums. In excess of US $600 million of biopolymers are expected to be sold in 2006.
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Petrochemical Route for Resin Synthesis
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Renewable Route to Resin Synthesis
• local supply, transport savings
• simpler refining
• sustainable resin supply
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Synthesis of Epoxides from Nonrenewable & Renewable resources
CH2 O CO
R1
CH O CO
R2
CH2 O CO
R3
CH2 O CO
CH O CO
R2
CH2 O CO
R3
(CH2)7 CH CH CH2 CH CH (CH2)4 CH3
O O
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Epoxidation of Double Bondwith in-situ generated peracetic acid
H2O2 + CH3COOH CH3COOOH + H2O
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Two Phase Model of Epoxidation with Ion Exchange Resin
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Reactor for Epoxidation
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Epoxidation of Canola as Function of Temperature and Time
0
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0 10 20 30 40 50 60
time in H
% o
f epo
xyda
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temperature 80temperature 60temperature 40
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Repeatability of Canola Epoxidation at 60° C
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time in H
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experiment 1experiment 2
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Canola Epoxidation at three Temperatures
y = 0.0501x
y = 0.1324x
y = 0.2244x
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0 5 10 15 20 25 30
time in H
ln (1
- %
EE)
temperature 40ratio 1 (60)temperature 80Linear (temperature 40)Linear (ratio 1 (60))Linear (temperature 80)
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Epoxy Equivalents of the EpoxidizedOils
1570.0162162-16.91022874.4old hemp
1601.9159162-16.41018874.4new hemp
2121.7118120-6.3934878.9canola
1374.31771850.1872873.2linseed
based on found IV valuedifference %foundliteraturedifference %foundliterature
calc. max. EE(g/oxiran oxygen)iodine value (IV)molecular weight (D)oil
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Comparison of some selected epoxidized materials
Note: No. 4 and 5 - reaction with: oil/HOAc/H2O2 = 1/1/2
ELO; 60 °C, 10 h62222Epox. Linseed-CEEFC5
ECO; 60 °C, 10 h71297Epox. Canola -CEEFC4
estimated, ESBO79234Lakroflex E23073
petrochemicaln/a339CTBN, Epon 580422
petrochemicaln/a181Araldite GY 260 IN1
Note% of the maximum
epoxidation achievableEE [ g/oxir. oxyg.]NameNo.
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Curing of low epoxidized LSO upto Gel Point
1 0 0 1 0 1 1 0 2 1 0 3 1 0 4 1 0 5 1 0 61 0 - 3
1 0 -2
1 0 -1
1 0 0
1 0 1
1 0 2
1 0 3
1 0 4
1 0 5
tim e [s ]
G' (
)
[P
a]
G" (
)
[P
a]
1 4 % te ta 0 .7 % 9 6 0 D y n t im e s w e e p te s t 1 ra d -s , 1 % s ta in 1 6 0 C 4 8 h rs
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Flexural Properties with Addition of Epoxidized oils
1.453Epoxy + 40% Epox. Linseed Rubber
2.077Epoxy + 30% Epox. Linseed Rubber
2.9102Epoxy + 20% Epox. Linseed Rubber
3.1116 Epoxy + 10% Epox. Linseed Rubber
3.3118Epoxy + 5% Epox. Linseed Rubber
1.352Epoxy + 40% Epox. Soy Rubber
1.975Epoxy + 30% Epox. Soy Rubber
2.9100Epoxy + 20% Epox. Soy Rubber
3.1115Epoxy + 10% Epox. Soy Rubber
3.2117Epoxy + 5% Epox. Soy Rubber
3.2116Neat epoxy
Flexural Modulus (GPa)
Flexural Strength (MPa)
System
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Toughening of Epoxy Resins I
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tora
ge M
odul
us (M
Pa)
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––––––– neat epoxy––––––– epoxy + 20% CTBN––––––– epoxy + 20% ELOR––––––– epoxy + 20% ESOR
Universal V3.9A TA Instruments
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Toughening of Epoxy Resins II97.82°C
93.80°C
80.36°C
84.75°C
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Mod
ulus
(MP
a)
25 50 75 100 125 150 175
Temperature (°C)
––––––– neat epoxy––––––– epoxy + 20% CTBN––––––– epoxy + 20% ELOR––––––– epoxy + 20% ESOR
Universal V3.9A TA Instruments
• Vegetable Oil based tougheners behave similarly to CTBN tougheners
• Cost of CTBN tougheners: $40-200/kg; Vegetable Oil Based: $4-10/kg
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Toughening of Epoxy Resins with Additives
Unmodified epoxy resin CTBN toughened
Epoxidized vegetable oil toughened resin
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Conclusion
Epoxidised oils can be used as plasticizers in certain thermosetting resins. Phase separation seem to limit the scope of use
Pre-curing of the epoxidised oils with suitable amines is necessary. The resulting product can be used to replace conventional rubber tougheners
Epoxidised oils as such cannot replace the room-temperature curing epoxies
We have developed a general procedure for epoxidation of vegetable oils, giving ~70% epoxidation. The 80% epoxidation seems to be a limit of this method
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END
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