with poly(methyl methacrylate) by UV radiation Bio-based thermoset plastics prepared from acrylated epoxidized soybean oil copolymerized with poly(methyl methacrylate) by UV radiation Presenter Miss.Narita Khundamri Adviser Assoc.Prof.Dr.Varaporn Tanrattanakul http://www.packworld.com/sustainability/bioplastics/world-demand-bioplastics-exceed-1-million-tons-2015 Department of Materials Science and Technology Prince of Songkla University

Introduction Petrochemicals The raw materials produced from petrochemicals are becoming more and more expensive.

Introduction Green house gases Petroleum-based polymers produces green house gases contributing to the problem of global warming.

Petroleum-based polymers Introduction Renewable resources Bio-based polymers Petroleum-based polymers

Epoxidized soybean oil (ESO) Acrylated epoxidized soybean oil Introduction Soybean oil Epoxidation Epoxidized soybean oil (ESO) *1 Acrylation Soybean oil (SO) http://health.zen-beautycare.com/health Acrylated epoxidized soybean oil (AESO) *2,3 *1 Tanrattanakul, V. & Saithai P. Applied Polymer Science. (2009). 114, 3057-3067. *2 Saithai, P., Tanrattanakul, V., Chinpa, W., Kaewtatip, K. & Dubreucq, E. Material Science Forum. (2011). 695, 320-323. *3 Saithai, P., Tanrattanakul, V., Dubreucq, E. & Lecomte, J. American Scientific Publishers. (2012). 19, 862-865.

Introduction Copolymers AESO Stronger polymers Copolymerization Polyester urethane acrylate J Mater Sci. (2010). 45, 1315-1320. Copolymerization by thermal heating Polystyrene Applied Polymer Science. (2001). 82, 703-723. Vinyl ester eXPRESS Polymer Letter. (2011). 5, 2-11. Stronger polymers p-tertiary butyl phenol furfural resin Appliedd Polymer Science. (2011). 120, 1707-1712. Poly(methyl methacrylate) Material Science Forum. (2011). 695, 320-323. American Scientific Publishers. (2012). 19, 862-865.

Introduction Photopolymerization Advantages of Photopolymerization UV irradiation Photoinitiator Advantages of Photopolymerization The speed of process is faster than thermal heating copolymerization. The loss of solvent is less than thermal heating copolymerization.

Objective To investigate the mechanical properties and determine characteristics of the AESO-co-PMMA copolymers prepared by using UV radiation.

(Use for removing inhibitor in MMA) Experimental Materials Darocur®1173 was kindly provided by O-BASF The Chemical Co. Ltd. (Photoinitiator) Epoxidized soybean oil from Viko-flex® 7170 Acrylic acid Methyl methacrylate (MMA) (comonomer) Hydroquinone (inhibitor) Triethylamine (catalyst) Aqueous sodium hydroxide solution Toluene (solvent) Anhydrous sodium sulfate (Use for removing inhibitor in MMA)

ESO+hydroquinone+triethylamine Experimental Method ESO+hydroquinone+triethylamine AESO AESO+MMA ESO: aâ= 1:15 110°C 7 hours 7 min (365 nm) UV irradiation

Results Degree of acrylation determined by 1H-NMR 52 mol% AESO (1) I5.8 is the intensity of a signal at  5.8 ppm and this corresponding to the acrylated protons (-CH) I0.9 is an intensity of a signal at  0.9 ppm that corresponded to the methyl protons (-CH3). 52 mol% AESO (Campanella et al., 2011) Figure 1. The 1H-NMR spectrum of the AESO showing the acrylate group at position 5.

Results Tensile properties Tensile toughness Stress  Strain Figure 2. Stress-strain curves of the AESO and AESO-co-PMMA copolymers containing different MMA contents.

Results Tensile properties c(εb) a(E) B(sb) Figure 3. Effect of the MMA content on the tensile properties of the AESO-co-PMMA copolymers: (a) Young’s modulus, (b) tensile strength and (c) strain at break.

Results Tear resistance Figure 4. Effect of the MMA content on the tear resistance of the AESO-co-PMMA copolymers.

Results Characterization by DMTA b a Figure 5. Effect of the MMA content on the dynamic mechanical thermal properties of the AESO-co-PMMA copolymers: (a) storage modulus and (b) tan .

Results Characterization by DSC Figure 6. DSC thermograms of the AESO, PMMA and AESO-co-PMMA copolymers.

Conclusions The results showed that the mechanical properties of the soybean oil-based plastic by copolymerization were successfully enhanced by incorporation of methyl methacrylate under UV radiation. The Young’s modulus, tear strength, Tg of AESO-co-PMMA copolymer increased as the methyl methacrylate content increased. The tensile strength, strain at break and tensile toughness had their maximum value when the methyl methacrylate content was 40 %; any further increase in the methyl methacrylate content decreased these properties.

Acknowledgements The authors would like to acknowledge the financial support from: The Research Development and Engineering (RD&E) fund through The National Nanotechnology Center (NANOTEC), The National Science and Technology Development Agency (NSTDA), Thailand (P-10-11333) to Prince of Songkla University.

Result & Discussion Copolymer formation determine by FTIR Table 1 FTIR assignment of the AESO-co-PMMA copolymer. Position Wavenumber (cm-1) Assignment (a) 3487 -OH stretching of AESO (b) 2920, 2851 -CH2- stretching of PMMA and –CH- stretching of AESO (c) 1722 -C=O carbonyl stretching (d) 1456 CH2=CH scissoring band of alkene at chain end of AESO (e) 1169-1256 C-O-C stretching of PMMA (f) 808, 723 C-C-O asymmetric band of AESO and PMMA Figure 2. The FTIR spectrum of the AESO, PMMA and AESO-co-PMMA.

Epoxidized soybean oil (ESO) Introduction Epoxidized Soybean oil Soybean oil (SO) Epoxidation Epoxidized soybean oil (ESO)

Epoxidized soybean oil (ESO) Acrylated Epoxidized soybean oil Introduction Acrylated Epoxidized Soybean oil Epoxidized soybean oil (ESO) Acrylation Acrylated Epoxidized soybean oil (AESO)

Result & Discussion Degree of acrylation determine by NMR The degree of acrylation in AESO (Nacrylated) was determined from equation (1) based on a 1H-NMR spectrum (Campanella et al., 2011). (1) I5.8 is the intensity of a signal at  5.8 ppm and this corresponding to the acrylated protons (-CH) I0.9 is an intensity of a signal at  0.9 ppm that corresponded to the methyl protons (-CH3).

Result & Discussion Characterization TGA Table 2 Thermal degradation of the AESO-co-PMMA sheets. MMA content (wt%) T5 (°C) T10 (°C) T50 (°C) 306 359 414 30 378 423 472 50 376 424 70 381 434 487 100 248 278 362 Note: T5, T10 and T10 are the temperatures at whioch 5%, 10% and 50% of weight loss occurred, respectively. Figure 5 TGA thermograms of the AESO, PMMA and AESO-co-PMMA copolymers.

Soluble fraction in THF (%) Soluble fraction in chloroform (%) Result & Discussion Characterization Soluble Fraction Table 3 Degree of soluble fraction of the AESO-co-PMMA sheets MMA content (wt%) Soluble fraction in THF (%) Soluble fraction in chloroform (%) 2.04 ± 0.41 2.00 ± 0.22 30 2.68 ± 0.29 3.01 ± 0.16 40 2.47 ± 0.31 2.83 ± 0.42 50 2.51 ± 0.31 2.75 ± 0.26 60 2.44 ± 0.73 2.55 ± 0.36 70 2.41 ± 0.31 3.21 ± 0.06 100 58.53 ± 4.01 77.88 ± 9.75

Swelling index in ethanol (%) Result & Discussion Characterization Swelling index Table 4 Swelling index of the the AESO-co-PMMA sheets MMA content (wt%) Swelling index in ethanol (%) 8.98 ± 0.06 30 14.49 ± 0.63 40 13.17 ± 0.60 50 16.67 ± 0.27 60 19.37 ± 0.63 70 19.38 ± 1.06 100 36.68 ± 1.54

Fernando Urena-Nunez et al., 2008

Copolymer PMMA AESO