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/wo
rld-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.
2
Introduction
Green house gases
Petroleum-based
polymers produces
green house gases
contributing to the
problem of global
warming.
3
Introduction
Renewable resources
Petroleum-based polymers
Bio-based polymers
4
Introduction
Soybean oil
O
H2C
O O
HC
O
H2C
O
O
O
O
O
O
Epoxidized soybean oil
(ESO) 1
*
Acrylation
O
H2C
O
O
O
O
HC
O
OH
O
O
Soybean oil (SO)
O
H2C
O
OH
http://health.zen-beautycare.com/health
O
O
O
OH
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.
5
Introduction
Copolymers
O
H2C
O
O
O
O
HC
O
OH
AESO
Copolymerization
by thermal
heating
O
O
O
O
H2C
O
O
O
OH
OH
Copolymerization
Polyester urethane acrylate
J Mater Sci. (2010). 45, 1315-1320.
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.
6
Introduction
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.
7
Objective
To investigate the mechanical properties and determine
characteristics of the AESO-co-PMMA copolymers
prepared by using UV radiation.
8
Experimental
Materials
 Epoxidized soybean oil
from Viko-flex® 7170
 Darocur®1173 was kindly provided
by O-BASF The Chemical Co. Ltd.
(Photoinitiator)
 Acrylic acid
 Methyl methacrylate (MMA)
(comonomer)
 Hydroquinone (inhibitor)
 Triethylamine (catalyst)
 Toluene (solvent)
 Aqueous sodium hydroxide
solution
 Anhydrous sodium sulfate
(Use for removing inhibitor in MMA)
9
Experimental
Method
AESO
ESO+hydroquinone+
triethylamine
ESO:
aâ= 1:15
AESO+MMA
110°C 7 hours
7 min (365 nm)
UV irradiation
10
Results
Degree of acrylation determined by 1H-NMR
N
52 mol% AESO
acrylated
 9I 
  5.8 
I 
 0.9 
(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).
(Campanella et al., 2011)
Figure 1. The 1H-NMR spectrum of the AESO
showing the acrylate group at position 5.
11
Results
Tensile properties
Tensile toughness
16
14
70 wt%
10
50 wt%
60 wt%
40 wt%
30 wt%
Stress
Stress (MPa)
12
8
0 wt%
6
4
Strain
2
0
0
1
2
3
4
5
6
7
8
9
10 11
12 13
Strain (%)
Figure 2. Stress-strain curves of the
AESO and AESO-co-PMMA copolymers
containing different MMA contents.
Tensile toughness 
𝑥
0
1
× (𝑎 + 𝑏) × ℎ
2
12
Results
Tensile properties
350
a(E)
228
250
267
261
278
12
205
200
150
95
100
50
0
0
30
40
50
60
70
MMA content (wt%)
Stress at break (MPa)
14
11.95
10.74
6
9.76
9.23
8.42
5.64
4
2
0
0
30
40
c(εb)
10
8
5.19
6
4.64
2.64
4
2
30
40
50
60
70
MMA content (%)
10
8
11.27
9.55
0
B(sb)
12
11.51
0
18
16
14
Strain at break (%)
E (MPa)
300
50
MMA content (%)
60
70
Figure 3. Effect of the MMA content
on the tensile properties of the AESOco-PMMA copolymers: (a) Young’s
modulus, (b) tensile strength and (c)
strain at break.
13
Results
Tear resistance
Figure 4. Effect of the MMA content on the tear resistance of the
AESO-co-PMMA copolymers.
14
Results
Characterization by DMTA
1.00E+11
a
1.00E+10
1.2
100 wt% 70 wt%
50 wt%
30 wt%
0 wt%
1.00E+09
1.00E+08
0.8
0.6
1.00E+07
0.4
1.00E+06
0.2
1.00E+05
0.0
-50
0
50
100
Temperature ( C)
b
100 wt% (92.4 C)
1.0
tan 
E' (Pa)
1.4
150
70 wt% (97.6 C)
50 wt% (79.4 C)
30 wt% (67.7 C )
0 wt% (35.3 C)
-50 -30 -10 10 30 50 70 90 110 130 150
Temperature ( C)
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 .
15
Results
Normalized Heat Flow Endo Up (W/g)
Characterization by DSC
2.35
Tg = 77.7 C 100 wt%
2.30
Tg = 49.5 C
2.25
70 wt%
50 wt%
Tg = 45.3 C
2.20
2.15
30 wt%
Tg = 38.5 C
2.10
2.05
0 wt%
Tg = 30.5 C
2.00
1.95
1.90
10
30
50
70
90
110
Temperature ( C)
Figure 6. DSC thermograms of the AESO, PMMA and AESO-coPMMA copolymers.
16
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.
17
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.
21
2
Result & Discussion
Copolymer formation determine by FTIR
Table 1 FTIR assignment of the AESOco-PMMA copolymer.
0 wt%
(d)
% Transmission
(a)
(e)
(b)
50 wt%
(c)
(a)
(g)
(f)
(d)
(e)
(b)
(c)
(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
(c)
(a)
(b)
3100
Wavenumber
(cm-1)
(f)
100 wt%
3600
(g)
2600
2100
1600
(d)
1100
(e)
600
Assignment
Position
wavenumber (cm-1)
Figure 2. The FTIR spectrum of the
AESO, PMMA and AESO-co-PMMA.
20
Introduction
Epoxidized Soybean oil
Soybean oil (SO)
Epoxidation
O
Epoxidized soybean oil
(ESO)
H2C
O
HC
O
H2C
O
O
O
O
O
O
O
21
Introduction
Acrylated Epoxidized Soybean oil
O
Epoxidized soybean oil
(ESO)
H2C
O
HC
O
H2C
O
O
O
O
O
O
O
Acrylation
O
H2C
Acrylated Epoxidized
soybean oil
(AESO)
O
O
O
O
HC
O
OH
O
O
O
H2C
O
O
O
O
OH
OH
22
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).
N
acrylated
 9I

5.8

 
 I

 0.9 
(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).
23
Result & Discussion
Characterization
TGA
Weight (%)
Table 2 Thermal degradation of the
AESO-co-PMMA sheets.
100 wt% 0 wt%
MMA content
T5 (°C) T10 (°C) T50 (°C)
(wt%)
70 wt%
30 wt%
50 wt%
Temperature ( C)
Figure 5 TGA thermograms of the
AESO, PMMA and AESO-co-PMMA
copolymers.
0
306
359
414
30
378
423
472
50
376
424
472
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.
24
Result & Discussion
Characterization
Soluble Fraction
Degree of soluble fraction (%) 
w2
 100
w1
Table 3 Degree of soluble fraction of the AESO-co-PMMA sheets
MMA content
(wt%)
Soluble fraction in THF Soluble fraction in chloroform
(%)
(%)
0
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
25
Result & Discussion
Characterization
Swelling index
Swelling index (%) 
wA  wB
 100
wB
Table 4 Swelling index of the the AESO-co-PMMA sheets
MMA content (wt%)
Swelling index in ethanol (%)
0
30
40
50
60
70
100
8.98 ± 0.06
14.49 ± 0.63
13.17 ± 0.60
16.67 ± 0.27
19.37 ± 0.63
19.38 ± 1.06
36.68 ± 1.54
26
O
CH3
C
C
CH3
O
hv
C
OH
+
OH
CH3
CH3
Darocure 1173
C
R2
R1
R
R
Fernando Urena-Nunez et al., 2008
Copolymer
PMMA
H3C
O
CH3
C
C
CH3
CH3
CH3
H2C
C
H2C
C
H2C
C
O
C
O
C
O
C
O
H2C
n
CH3
O
C
C
O
CH3
CH2
O
O
CH2
O
O
R
O
CH3
R
H2C
C
H
CH3
CH
O
CH
OH
(CH2)7
C
O
HC
C
O
C
O
H3C (H2C)7
CH3
H2C
CH2
O
C
H
CH2
O
C
O
(CH2)7
HC
CH
(CH2)7
CH3
CH
(CH2)7
CH3
OH
C
(CH2)7
HC
O
AESO
HO
O
CH2
O
H
C
C
O
28