Plant Based Resins for Fibre Composites Dr. Pavel Faigl Dr. David - - PowerPoint PPT Presentation

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 of

thermosetting 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 fibre reinforcements

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

• il 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 C O R1 CH O C O R2 CH2 O C O R3

CH2 O C O CH O C O R2 CH2 O C O R3 (CH2)7 CH CH CH2 CH CH (CH2)4 CH3 O O

Epoxidation of Double Bond

with 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

10 20 30 40 50 60 70 80 90 10 20 30 40 50 60 time in H % of epoxydation temperature 80 temperature 60 temperature 40

Repeatability of Canola Epoxidation at 60° C

10 20 30 40 50 60 70 1 2 3 4 5 6 7 8 9 time in H % of epoxydation experiment 1 experiment 2

Canola Epoxidation at three Temperatures

y = 0.0501x y = 0.1324x y = 0.2244x 1 2 3 4 5 6 5 10 15 20 25 30 time in H ln (1 - %EE) temperature 40 ratio 1 (60) temperature 80 Linear (temperature 40) Linear (ratio 1 (60)) Linear (temperature 80)

Epoxy Equivalents of the Epoxidized Oils

157 0.0 162 162

• 16.9

1022 874.4

• ld hemp

160 1.9 159 162

• 16.4

1018 874.4 new hemp 212 1.7 118 120

• 6.3

934 878.9 canola 137 4.3 177 185 0.1 872 873.2 linseed based on found IV value difference % found literature difference % found literature

• calc. max. EE

(g/oxiran oxygen) iodine value (IV) molecular weight (D)

• il

Comparison of some selected epoxidized materials

Note: No. 4 and 5 - reaction with: oil/HOAc/H2O2 = 1/1/2 ELO; 60 °C, 10 h 62 222

• Epox. Linseed-CEEFC

5 ECO; 60 °C, 10 h 71 297

• Epox. Canola -CEEFC

4 estimated, ESBO 79 234 Lakroflex E2307 3 petrochemical n/a 339 CTBN, Epon 58042 2 petrochemical n/a 181 Araldite GY 260 IN 1

Note

% of the maximum epoxidation achievable

EE [ g/oxir. oxyg.] Name No.

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 6 1 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' ( ) [Pa] G" ( ) [Pa]

1 4 % te ta 0 .7 % 9 6 0 D y n tim 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

1.4 53 Epoxy + 40% Epox. Linseed Rubber 2.0 77 Epoxy + 30% Epox. Linseed Rubber 2.9 102 Epoxy + 20% Epox. Linseed Rubber 3.1 116 Epoxy + 10% Epox. Linseed Rubber 3.3 118 Epoxy + 5% Epox. Linseed Rubber 1.3 52 Epoxy + 40% Epox. Soy Rubber 1.9 75 Epoxy + 30% Epox. Soy Rubber 2.9 100 Epoxy + 20% Epox. Soy Rubber 3.1 115 Epoxy + 10% Epox. Soy Rubber 3.2 117 Epoxy + 5% Epox. Soy Rubber 3.2 116 Neat epoxy Flexural Modulus (GPa) Flexural Strength (MPa) System

Toughening of Epoxy Resins I

500 1000 1500 2000 2500 3000

Storage Modulus (MPa)

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 II

97.82°C 93.80°C 80.36°C 84.75°C

50 100 150 200 250

Loss Modulus (MPa)

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