Sustainable Polymers: Thermosets

from Agricultural Oils

Michael R. Kessler
School of Mechanical and
Materials Engineering
Washington State University

Co-authors: Richard Larock, Yongshang Lu, Ying Xia, Rafael Quirino, Tom
Garrison, and Prashanth Badrinarayanan
 Polymer Composites Research Group

Funding:
•National Science Foundation
•Consortium for Plant Biotechnology Research
•ISU Plant Sciences Institute, Grow Iowa Values Fund
•UNI Recycling and Reuse Tech. Transfer Center
•Industry
 Overview of Research
Multi-
functional
composites

Processing and Bio-renewable

Polymer Nano-
polymers and
composites characterization composites
of polymer
composites

Polymer
matrix Rheology and
composites for thermal
extreme analysis
environments
 Overview of Research
Multi-
functional
composites

Processing and Bio-renewable

Polymer Nano-
polymers and
composites characterization composites
of polymer
composites

Polymer
matrix Rheology and
composites for thermal
extreme analysis
environments
 Overview of Research
Multi-
functional
composites

Processing and Bio-renewable

Polymer Nano-
polymers and
composites characterization composites
of polymer
composites

Polymer
matrix Rheology and
composites for thermal
extreme analysis
environments
Nearly two orders of magnitude
increase in toughness with just
0.4 wt% Carbon Nanotubes
 Overview of Research
Multi-
Structural Capacitors
functional
composites

Processing and Bio-renewable

Polymer Nano-
polymers and
composites characterization Self-healing Composites
composites
of polymer
composites

Polymer
matrix Rheology and
composites for thermal
extreme analysis
environments
 Overview of Research
Multi-
functional
composites

Processing and Bio-renewable

Polymer Nano-
polymers and
composites characterization composites
of polymer
composites

Polymer
matrix Rheology and
composites for thermal
extreme analysis
environments
 Outline
• Plastics from vegetable oils (thermosets)
– Free radical polymerization
– Cationic polymerization
– Ring-opening metathesis polymerization
• Composites
• Polyurethane Coatings
 Advantages of Natural Oils

Million
Billion Metric
 Readily available on a huge scale. Pounds Tons
 Very inexpensive.

 Natural and renewable.

 High purity.

 Relatively high molecular weight.

 Can be genetically engineered. U.S. Soybean Oil Production. Source: USDA

 Many structurally related natural oils are readily available.

 Soybean Oil Structure

CH3 (CH2) 7 CH=CH(CH2) 7 CO2CH2

CH3 (CH2) 4CH=CHCH2 CH=CH(CH2) 7 CO2CH

CH3CH2CH =CHCH2CH =CHCH2 CH=CH(CH2) 7 CO2CH2

Oleic acid 22%

Linoleic acid 54%
Linolenic acid 8%
 Natural and Conjugated Oils
Oil C=C Bonds % Composition
Conjugated No. C18:1 C18:2 C18:3

Regular soy oil (SOY) no 4.5 22 54 8

LoSatSoy oil (LSS) no 5.1 20 64 9
Conjugated LSS (CLS) yes 5.1 20 64 9
Linseed oil (LIN) no 5.8 19 15 57
Conjugated linseed oil (CLIN) yes 5.8 19 15 57
Tung oil (TUN) yes 8.2 5 7 85a
a -Eleostearic acid (9,11,13-octadecatrienoic acid)
CH2 CH CH CH2
CH2 CH CH CH2 CH CH CH2
CH2 CH CH CH2 CH CH CH2 CH CH CH2

In SOY and LSS oils

CH2 CH CH CH2
CH2 CH CH CH CH CH2
CH2 CH CH CH CH CH CH CH2

In CLS, C100LIN, C87LIN and TUN oils

 Free Radical Polymerization
CH CH CO2

Me Me
CH CH CO2 +
+ CN + NC C N N C CN
Me Me
CH CH CO2

C100LIN or CLS AN DVB AIBN

(initiator)
60 oC 12 hrs
70 oC 12 hrs
80 oC 12 hrs
90 oC 12 hrs O
110 oC 12 hrs O C CH CH
120 oC 12 hrs

O O
C O C O

CH CH2 CH CH CH CH2 CH CH2 CH CH

n n

CN

CH CH2 CH CH2
 Free Radical Polymerization of
Conjugated Soybean Oil
Tg Tan T10 T50 Tmax % %
Sample (ºC) Delta (ºC) (ºC) (ºC) Sol Insol

CLS40-AN54-DVB6-AIBN1 102 0.36 - - - 1.6 98.4

CLS50-AN45-DVB5-AIBN1 95 0.35 - - - 2.1 97.9
CLS60-AN36-DVB4-AIBN1 74 0.36 - - - 4.5 95.5
CLS70-AN27-DVB3-AIBN1 49 0.36 - - - 6.8 93.2

Tg Tan T10 T50 Tmax % %

Sample (ºC) Delta (ºC) (ºC) (ºC) Sol Insol

CLS40-AN54-DCP6-AIBN1 107 0.49 389 488 458 0.9 99.1

CLS50-AN45-DCP5-AIBN1 84 0.45 419 484 490 1.8 98.2
CLS60-AN36-DCP4-AIBN1 65 0.46 426 491 499 2.7 97.3
CLS70-AN27-DCP3-AIBN1 32 0.47 433 502 524 7.5 92.5
DCP = dicyclopentadiene
 Cationic Polymerization
CH CH CO2

CH CH CO2 + +

CH CH CO2
ST DVB
Triglyceride

.
cat. BF3 OEt2
25 o C / 12h
(BFE) 60 o C / 12h
110 o C / 24h

O
O C CH CH

O O
C O C O

CH2 CH CH CH n CH CH n CH2 CH CH2 CH

m m
 Mechanical Properties of Soybean
Oil Polymers
Characteristics of soybean oil polymers
Polymer Tg e Tmaxa Eb bc bd Toughness
(oC) (mol/m3 (oC) (MPa) (MPa) (%) (MPa)
)
Polyethylene (LDPE) -68 - 355 370 9.6 46 5.2
Polystyrene 90 - 420 1330 30.3 4 0.5

CLS45-ST47-DVB00-(NFO5-BFE3) e 10 1.0102 448 12 1.3 300 2.0

CLS45-ST32-DVB15-(NFO5-BFE3) f 76 2.2103 475 225 11.5 41 4.0
CLS35-ST39-DVB18-(NFO5-BFE3) g 82 3.4103 477 500 21.0 3 0.8

SOY45-ST32-DVB15-(NFO5-BFE3) 68 1.8102 468 71 4.1 57 1.7

LSS45-ST32-DVB15-(NFO5-BFE3) 61 5.3102 470 90 6.0 64 2.9
CLS45-ST32-DVB15-(NFO5-BFE3) 76 2.2103 475 225 11.5 41 4.0
a
The temperature at the maximum degradation rate
b
Young's modulus
c
Break strength
d
Elongation at break
e
A typical elastomer
f
A ductile plastic
g
A rigid plastic
 Polymers from Other Vegetable Oils

 All oils have a

triglyceride structure
composed primarily of
Percentages of reacted oil

oleic acid, linoleic acid

and linolenic acid.

 Generally, higher
unsaturation results in
a plastic with higher
mechanical properties.
 Polymers from Other Vegetable Oils

Table. Tensile mechanical p roperties of other natural oil-based plastics

Samples E b b Toughness
(MPa) (MPa) (%) (MPa)
PNT45-ST32-DVB15 -(NFO5-BFE3) 32 2.5 20.0 0.27
SES45-ST32-DVB15 -(NFO5-BFE3) 48 3.8 48.1 1.46
COR45-ST32-DVB15 -(NFO5-BFE3) 48 4.0 51.7 1.64
SUN45-ST32-DVB15 -(NFO5-BFE3) 49 5.1 55.7 1.78
SAF45-ST32-DVB15 -(NFO5-BFE3) 76 4.5 48.1 1.79
WNT45-ST32-DVB15 -(NFO5-BFE3) 85 6.1 62.1 2.97
LIN45-ST32-DVB15 -(NFO5-BFE3) 75 7.0 60.4 3.22

• The agricultural oil-based polymers exhibit characteristics ranging from

soft to tough plastics.

• Generally, a higher degree of unsaturation in the oil results in a plastic

with higher mechanical properties.
 Ring Opening Metathesis
Polymerization of Oils

Dilulin
O
O
O
O
O

0.25 wt % Grubbs II

1 h 65 oC, 3 h 150 oC

O n
O
O
O
O

 Dilulin is found to have approximately 1 bicyclic unit per triglyceride.

 1H NMR and FTIR indicate the presence of norbornene-like hydrogens.
 Ring Opening Metathesis
Polymerization of Oils
Characteristics of Oil-Based ROMP Copolymers

Tg υe E' T10 T50 Tmax

Specimen % sol
(oC) (mol/m3) (MPa) (oC) (oC) (oC)

Dil50-DCPD50 36 1377 228 427 461 462 21

Dil70-DCPD30 -9 1299 6.35 414 453 462 26
Dil90-DCPD10 -30 866 1.88 362 440 459 28
Dil100-DCPD0 -29 715 - 376 438 459 28
Pure Dilulin - - - 301 415 451 -
υe , crosslink density according to rubber theory of elasticity
E', storage modulus at 25 oC
Tmax, temperature of maximum degradation
Ring Opening Metathesis
Polymerization of Oils
 Ring Opening Metathesis
Polymerization of Oils

NCO100 E’ at
Tg υe
1000 NCO80NCA20 Polymer o 25 oC
( C) (mol/m3)a
NCO60NCA40 (MPa)
NCO40NCA60
NCO20NCA80 NCO100 -17.1 318 2.4
Storage Modulus (MPa)

NCA100
NCO80NCA20 -6.2 740 5.7
100
NCO60NCA40 14.6 1664 27.8

NCO40NCA60 27.5 2790 130.0

10 NCO20NCA80 49.1 4418 583.4

NCA100 65.4 6028 831.9

a) Crosslink densities have been calculated at

-50 0 50 100 150
temperatures 50 oC above the Tg according
o
Temperature ( C) to the equation:

 An increase in the amount of NCA increases the Tg, the crosslink density,
and the room temperature storage modulus
 Outline

• Plastics from vegetable oils (thermosets)

– Free radical polymerization
– Cationic polymerization
– Ring-opening metathesis polymerization
• Composites
• Polyurethane Coatings
 Soy-Glass Fiber Composites
Mechanical properties
3000
SOY50-ST25-DVB10-NFO10-BFE5
LSS50-ST25-DVB10-NFO10-BFE5
 Incorporating glass fiber
2500 LSS50-ST20-DVB20-NFO5-BFE5
into the soy-based polymer
Young's modulus / MPa

2000
results in good composites
1500 with improved properties.
1000

500
 Increasing crosslinking of
0
0 10 20 30 40 50 the polymer matrix can
90
Glass fiber content / wt %
dramatically increase the
SOY50-ST25-DVB10-NFO10-BFE5
LSS50-ST25-DVB10-NFO10-BFE5
mechanical properties.
75 LSS50-ST20-DVB20-NFO5-BFE5
Tensile strength / MPa

60
 Fiber surface modification
45
and compatibilization efforts
30 are currently underway
15

0
0 10 20 30 40 50
Glass fiber content / wt %
 Soy-Organomodified Clay
Nanocomposites
Mechanical properties
700 70
CSOY50-ST25-DVB10-NFO10-BFE5 CSOY50-ST25-DVB10-NFO10-BFE5
CLS50-ST25-DVB10-NFO10-BFE5 CLS50-ST25-DVB10-NFO10-BFE5
600 60
Compressive modulus / MPa

Compressive strength / MPa

500 50

400 40

300 30

200 20

100 10

0 0
0 1 2 3 4 5 0 1 2 3 4 5
Clay content / wt % Clay content / wt %

 1-2 wt % clay can significantly increase the mechanical properties.

 CLS affords better mechanical properties than CSOY.

 Linseed Oil-Natural Fiber
Composites

Mechanical properties

CLIN-Kenaf Fiber CLIN-Woodflour

2500 30 1250 30
Matrix: CLIN50-ST15-DVB25-NFO6-BFE4 Matrix: CLIN50-ST15-DVB25-NFO5-BFE5
Modulus Modulus

Flexural strength / MPa

25

Flexural strength / MPa

Strength

Flexural modulus / MPa

Flexural modulus / MPa

Strength
2000 25 1000
20

1500 20 750 15

10
1000 15 500
5

500 10 250 0
0 10 20 30 40 50
0 10 20 30 40 50
Woodflour content / wt %
Kenaf fiber content / wt %

 The modulus increases linearly with increasing natural fiber content.

 The strength decreases a bit due to poor interfacial adhesion.
Fiber surface modification and compatibilization efforts are underway
 Tung Oil-Spent Germ Biocomposites

Matrix: TUN50-BMA35-DVB15-TBPO5 Fillers: Spent Germ (~ 50 wt %)

Tensile test Flexural test
14
1100
550 18
1000

Flexural Strength (MPa)

12
500
Tensile Strength (MPa)

900 15

Modulus (MPa)
Modulus (MPa)
10 450 800
12

400 700
8
9
600
350
6
500 6
300
400
4

h
h

h
h
h
ed

es

es
es

es
es
es
h
h

M
d

iev

M
M

M
M
M
h
es
es

es

es
ve

es
es

0
ns

80
0

60
0
0
M
M

>6
M

M
ie

>8
>4
>2
M

x
x
ns

0
0

80
60
0
>4
>2

60
40
>6

>8
U

x
x

60
40

 Incorporating spent germ can significantly increase the mechanical properties

 Particle size plays an important role in improving the materials performance
 Corn Stover Biocomposites
6 1200
8 1500

1000
5

Young's Modulus (MPa)

7 1350
Tensile Strength (MPa)

Young's Modulus (MPa)

Tensile Strength (MPa)
800

4
6 1200
600

3
400 5 1050

2 200
4 900
20 30 40 50 60 70 80
CSOY- CSOY- CSOY- CLIN- CLIN- CLIN-
Amount of Corn Stover (wt %) DVB10 DVB15 DVB20 DVB10 DVB15 DVB20

Matrix: CSOY50-BMA35-DVB15-TBPO5 Matrix: (CSOY or CLIN)50-(BMA + DVB)50-TBPO5

Filler: 2 mm Corn Stover Filler: 2 mm Corn Stover (70 wt %)
 Increasing the corn stover, up to 70 wt %, results in a considerable increase in
the strength and stiffness of the composites.
 A higher crosslinked matrix, achieved by increasing the amount of the crosslinker,
DVB, or replacing CSOY with the more highly unsaturated oil CLIN gives
enhanced mechanical properties.
 Wheat Straw Biocomposites
2000 12 1950

8
1800

Young's Modulus (MPa)

Young's Modulus (MPa)
Tensile Strength (MPa)
Tensile Strength (MPa)

1600 10 1800
6

1400

4
1200 8 1650

1000
2

800 6 1500
50 60 70 80 90 0 5 10 15
Amount of Wheat Straw (wt %) Amount of Maleic Anhydride (wt %)

Matrix: CLIN50-BMA35-DVB15-TBPO5 Matrix: (CLIN)50-(BMA + MA)35-DVB15-TBPO5

Filler: 2 mm Wheat Straw Filler: 2 mm Wheat Straw (80 wt %)

 Good mechanical properties can be maintained using as much as 80 wt % of wheat

straw.
 Maleic anhydride (MA) is an effective compatibilizer between the filler and matrix
and significant increases in the mechanical properties result by the addition of MA.
 Outline
• Plastics from vegetable oils (thermosets)
– Free radical polymerization
– Cationic polymerization
– Ring-opening metathesis polymerization
• Composites
• Polyurethane Coatings
 Vegetable Oil-Based Dispersions
NCO O
HO OCH3
O HO OCH3 O OH
O 4
4 O O O OH OH
3 OCN
O HO OCH3
MSOL IPDI DMPA
Heat
HOOC
COOH
HOOC HOOC

O OCH3
O O OCH3 O
O 4
4 O O O
3
O O OCH3

NEt3 COOH

CO2NHEt3 CO2NHEt3
Water
CO2NHEt3

CO2NHEt3
O OCH3
O O OCH3 O
O 4
4 O O O
3
O O OCH3

CO2NHEt3

Soybean Oil-Based Waterborne Polyurethane Dispersion (SPU)

 Vegetable Oil-Based Dispersions

(4.0)

(2.8)

(2.4)
 Vegetable Oil-Based Dispersions
100

r = 0.998
 The Tg of the SPU films increases
Tg values from DMA
80

60
linearly with an increase in the OH
Tg ( C )

functionality.
o

40 r = 0.982
Tg values from DSC

20
 The mechanical properties of the
0 SPU films increase with the OH
140 160 180 200
OH number ( mg KOH/g ) functionality.

 The mechanical properties of the

SPU films change from those of
an elastomer to a ductile polymer
and eventually to a hard plastic
with an increase in the OH
functionality.
Vegetable Oil-Based Cationic PU
Dispersions

33
 Vegetable Oil-Based Cationic PU
Dispersions

2 3 4

5 6

Zone of inhibition for Salmonella Minnesota R613.

1) acetic acid control, 2) PU-MDEA, 3) PU-EDEA, 4) PU-
PDE, 5) PU-MDEA-TEA, 6) PU-EDTE.

 PU-MDEA (2) and PU-EDEA (3) show best antibacterial properties, because their
smaller methyl and ethyl side chains on N atoms allow greater penetration of these
polymers into cells.

34
 Summary
• Industrially promising biopolymers ranging from elastomers to
rigid plastics have been prepared.

• These biomaterials have excellent thermal and mechanical

properties.

• Work with other comonomers, oils and processes is

underway.

• Biocomposites can be made from a variety of materials.

• Work on biobased coatings and adhesives is promising.

Questions?/Discussion
 Extra Slide 1
Conjugation of Natural Oils
CH3(CH2)4 CH2 (CH2)7CO2R 0.1 % [RhCl(C8H14)2]2
0.4 % (p-CH3C6H4)3P
C C C C Conjugated
0.8 % SnCl2. 2H2O
H H H H Ethanol
Oil
60 oC, 1 day

Oil % Conjugation
Linseed 100
Walnut 85
Safflower 91
Sunflower 82
Soy 100
Corn 78
Sesame 74
70
Peanut

J. Am. Oil. Chem. Soc. 78, 447 (2001)

 Damping Properties of Soybean Oil
Polymers

Table. Damping results of soy bioplastics measured by DMA at 1 Hz

Polymer Tg (tan )max (tan )rt T at tan  tan  area
(oC) > 0.3 ( oC) TA (K) a
PU-based IPNb 50-40 0.53-0.70 0.44-0.69 90-120 41-66

SOY45-ST42-DVB5 -(NFO5-BFE3) 36 3.90 1.36 83 124

SOY45-ST37-DVB10 -(NFO5-BFE3) 44 1.46 0.60 110 57

SOY45-ST32-DVB15 -(NFO5-BFE3) 68 0.85 0.32 90 48

LSS55-ST25-DVB12 -(NFO5-BFE3) 32 1.00 0.96 89 50

LSS45-ST37-DVB10 -(NFO5-BFE3) 48 1.51 0.74 91 75

CLS45-ST37-DVB10-(NFO5-BFE3) 60 1.50 0.30 93 77

a
The backg round w as corrected.
b
Data for typical polyure thane damping materials [J. Appl. Polym. Sci. 74, 28 (1999 )].