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 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 O O O O CH 2 O C R 1 (CH 2 ) 7 CH CH CH 2 CH CH (CH 2 ) 4 CH 3 CH 2 O C O O CH O C R 2 CH O C R 2 O O CH 2 O C R 3 CH 2 O C R 3

Epoxidation of Double Bond with in-situ generated peracetic acid H 2 O 2 + CH 3 COOH CH3COOOH + H 2 O

Two Phase Model of Epoxidation with Ion Exchange Resin

Reactor for Epoxidation

Epoxidation of Canola as Function of Temperature and Time 90 80 70 60 % of epoxydation 50 temperature 80 temperature 60 temperature 40 40 30 20 10 0 0 10 20 30 40 50 60 time in H

Repeatability of Canola Epoxidation at 60 ° C 70 60 50 % of epoxydation 40 experiment 1 experiment 2 30 20 10 0 0 1 2 3 4 5 6 7 8 9 time in H

Canola Epoxidation at three Temperatures 6 y = 0.2244x 5 4 temperature 40 ln (1 - %EE) ratio 1 (60) y = 0.1324x temperature 80 3 Linear (temperature 40) Linear (ratio 1 (60)) Linear (temperature 80) 2 y = 0.0501x 1 0 0 5 10 15 20 25 30 time in H

Epoxy Equivalents of the Epoxidized Oils calc. max. EE oil molecular weight (D) iodine value (IV) (g/oxiran oxygen) literature found difference % literature found difference % based on found IV value linseed 873.2 872 0.1 185 177 4.3 137 canola 878.9 934 -6.3 120 118 1.7 212 new hemp 874.4 1018 -16.4 162 159 1.9 160 old hemp 874.4 1022 -16.9 162 162 0.0 157

Comparison of some selected epoxidized materials % of the maximum No. Name EE [ g/oxir. oxyg.] epoxidation achievable Note 1 Araldite GY 260 IN 181 n/a petrochemical 2 CTBN, Epon 58042 339 n/a petrochemical 3 Lakroflex E2307 234 79 estimated, ESBO ECO; 60 ° C, 10 h 4 Epox. Canola -CEEFC 297 71 ELO; 60 ° C, 10 h 5 Epox. Linseed-CEEFC 222 62 Note: No. 4 and 5 - reaction with: oil/HOAc/H2O2 = 1/1/2

Curing of low epoxidized LSO upto Gel Point 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 1 0 5 1 0 4 1 0 3 1 0 2 ) [Pa] G" ( 1 0 1 ) [Pa] G' ( 1 0 0 1 0 -1 1 0 -2 1 0 -3 1 0 1 1 0 2 1 0 3 1 0 4 1 0 5 1 0 0 1 0 6 tim e [s ]

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

Toughening of Epoxy Resins I 3000 ––––––– neat epoxy ––––––– epoxy + 20% CTBN ––––––– epoxy + 20% ELOR ––––––– epoxy + 20% ESOR 2500 2000 Storage Modulus (MPa) 1500 1000 500 0 0 50 100 150 Universal V3.9A TA Instruments Temperature (°C)

Toughening of Epoxy Resins II 250 ––––––– neat epoxy 97.82°C ––––––– epoxy + 20% CTBN ––––––– epoxy + 20% ELOR ––––––– epoxy + 20% ESOR 200 84.75°C 93.80°C 80.36°C Loss Modulus (MPa) 150 100 50 0 25 50 75 100 125 150 175 Universal V3.9A TA Instruments Temperature (°C) • 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 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 Epoxidised oils as such cannot replace the room-temperature curing epoxies Pre-curing of the epoxidised oils with suitable amines is necessary. The resulting product can be used to replace conventional rubber tougheners Epoxidised oils can be used as plasticizers in certain thermosetting resins. Phase separation seem to limit the scope of use

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