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

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

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.

Petrochemical Route for Resin Synthesis

Renewable Route to Resin Synthesis

• local supply, transport savings

• simpler refining

• sustainable resin supply

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

Epoxidation of Double Bondwith in-situ generated peracetic acid

H2O2 + CH3COOH CH3COOOH + H2O

Two Phase Model of Epoxidation with Ion Exchange Resin

Reactor for Epoxidation

Epoxidation of Canola as Function of Temperature and Time

0

10

20

30

40

50

60

70

80

90

0 10 20 30 40 50 60

time in H

% o

f epo

xyda

tion

temperature 80temperature 60temperature 40

Repeatability of Canola Epoxidation at 60° C

0

10

20

30

40

50

60

70

0 1 2 3 4 5 6 7 8 9

time in H

% o

f epo

xyda

tion

experiment 1experiment 2

Canola Epoxidation at three Temperatures

y = 0.0501x

y = 0.1324x

y = 0.2244x

0

1

2

3

4

5

6

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)

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

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.

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

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

Toughening of Epoxy Resins I

0

500

1000

1500

2000

2500

3000S

tora

ge M

odul

us (M

Pa)

0 50 100 150

Temperature (°C)

––––––– neat epoxy––––––– epoxy + 20% CTBN––––––– epoxy + 20% ELOR––––––– epoxy + 20% ESOR

Universal V3.9A TA Instruments

Toughening of Epoxy Resins II97.82°C

93.80°C

80.36°C

84.75°C

0

50

100

150

200

250

Loss

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

Toughening of Epoxy Resins with Additives

Unmodified epoxy resin CTBN toughened

Epoxidized vegetable oil toughened resin

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

END