Slide 1

Department of Materials Science and Technology Prince of Songkla University Presenter Miss.Narita Khundamri Adviser Assoc.Prof.Dr.Varaporn Tanrattanakul

Slide 2

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

Slide 3

Green house gases Introduction 3 Petroleum-based polymers produces green house gases contributing to the problem of global warming.

Slide 4

Renewable resources Introduction 4 Petroleum-based polymers Bio-based polymers

Slide 5

Soybean oil http://health.zen-beautycare.com/health Epoxidized soybean oil (ESO) Acrylated epoxidized soybean oil (AESO) Soybean oil (SO) Introduction 5 Epoxidation Acrylation *1*1 * 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. * 2,3

Slide 6

Copolymers AESO Copolymerization by thermal heating Introduction 6 Polystyrene Applied Polymer Science. (2001). 82, 703-723. Polyester urethane acrylate J Mater Sci. (2010). 45, 1315-1320. Vinyl ester eXPRESS Polymer Letter. (2011). 5, 2-11. p- 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. Stronger polymers Copolymerization

Slide 7

Photopolymerization UV irradiation Introduction 7 Advantages of Photopolymerization The speed of process is faster than thermal heating copolymerization. The loss of solvent is less than thermal heating copolymerization. Photoinitiator

Slide 8

To investigate the mechanical properties and determine characteristics of the AESO-co-PMMA copolymers prepared by using UV radiation. Objective 8

Slide 9

Experimental Materials Acrylic acid Darocur 1173 was kindly provided by O-BASF The Chemical Co. Ltd. (Photoinitiator) Methyl methacrylate (MMA) (comonomer) Hydroquinone (inhibitor) Triethylamine (catalyst) Aqueous sodium hydroxide solution Anhydrous sodium sulfate Epoxidized soybean oil from Viko-flex 7170 Toluene (solvent) 9 (Use for removing inhibitor in MMA)

Slide 10

Method Experimental 10 7 min (365 nm) UV irradiation ESO: a = 1:15 110 C 7 hours AESO+MMA AESO ESO+hydroquinone+ triethylamine

Slide 11

Figure 1. The 1 H-NMR spectrum of the AESO showing the acrylate group at position 5. Results 11 Degree of acrylation determined by 1 H-NMR I 5.8 is the intensity of a signal at 5.8 ppm and this corresponding to the acrylated protons (-CH) I 0.9 is an intensity of a signal at 0.9 ppm that corresponded to the methyl protons (-CH 3 ). 52 mol% AESO (1) (Campanella et al., 2011)

Slide 12

Figure 2. Stress-strain curves of the AESO and AESO-co-PMMA copolymers containing different MMA contents. 12 Stres s Strai n Tensile toughness Results Tensile properties

Slide 13

Figure 3. Effect of the MMA content on the tensile properties of the AESO- co-PMMA copolymers: (a) Youngs modulus, (b) tensile strength and (c) strain at break. 13 a(E) B( b ) c( b ) Tensile properties Results

Slide 14

Figure 4. Effect of the MMA content on the tear resistance of the AESO-co-PMMA copolymers. 14 Tear resistance Results

Slide 15

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 . Characterization by DMTA a b 15 Results

Slide 16

Figure 6. DSC thermograms of the AESO, PMMA and AESO-co- PMMA copolymers. Results Characterization by DSC 16

Slide 17

The Youngs modulus, tear strength, T g of AESO-co-PMMA copolymer increased as the methyl methacrylate content increased. Conclusions 17 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. 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.

Slide 18

21 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.

Slide 19

2

Slide 20

Figure 2. The FTIR spectrum of the AESO, PMMA and AESO-co-PMMA. Result & Discussion Copolymer formation determine by FTIR Table 1 FTIR assignment of the AESO- co-PMMA copolymer. 20

Slide 21

Epoxidized Soybean oil Soybean oil (SO) Epoxidized soybean oil (ESO) Epoxidation Introduction 21

Slide 22

Acrylated Epoxidized Soybean oil Epoxidized soybean oil (ESO) Acrylated Epoxidized soybean oil (AESO) Acrylation Introduction 22

Slide 23

The degree of acrylation in AESO (N acrylated ) was determined from equation (1) based on a 1 H-NMR spectrum (Campanella et al., 2011). (1) I 5.8 is the intensity of a signal at 5.8 ppm and this corresponding to the acrylated protons (-CH) I 0.9 is an intensity of a signal at 0.9 ppm that corresponded to the methyl protons (-CH 3 ). Degree of acrylation determine by NMR Result & Discussion 23

Slide 24

Figure 5 TGA thermograms of the AESO, PMMA and AESO-co-PMMA copolymers. Table 2 Thermal degradation of the AESO-co-PMMA sheets. Note: T 5, T 10 and T 10 are the temperatures at whioch 5%, 10% and 50% of weight loss occurred, respectively. Result & Discussion TGA Characterization 24

Slide 25

Result & Discussion Soluble FractionCharacterization Table 3 Degree of soluble fraction of the AESO-co-PMMA sheets 25

Slide 26

Table 4 Swelling index of the the AESO-co-PMMA sheets Result & Discussion Swelling index Characterization 26

Slide 27

R R Fernando Urena-Nunez et al., 2008

Slide 28

Copolymer 28 PMMA AESO