1. 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

2. 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

3. Overview of Research
Processing and characterization of polymer composites
Multi-functional composites
Polymer matrix composites for extreme environments
Polymer Nano-composites
Bio-renewable polymers and composites
Rheology and thermal analysis

4. Overview of Research
Processing and characterization of polymer composites
Multi-functional composites
Polymer Nano-composites
Bio-renewable polymers and composites
Rheology and thermal analysis
Polymer matrix composites for extreme environments

5. Overview of Research
Processing and characterization of polymer composites
Multi-functional composites
Bio-renewable polymers and composites
Rheology and thermal analysis
Polymer matrix composites for extreme environments
Polymer Nano-composites
Nearly two orders of magnitude increase in toughness with just 0.4 wt% Carbon Nanotubes

6. Structural Capacitors Self-healing Composites
Overview of Research
Multi-functional composites
Structural Capacitors
Self-healing Composites
Processing and characterization of polymer composites
Bio-renewable polymers and composites
Rheology and thermal analysis
Polymer matrix composites for extreme environments
Polymer Nano-composites

7. Overview of Research
Processing and characterization of polymer composites
Multi-functional composites
Rheology and thermal analysis
Polymer matrix composites for extreme environments
Polymer Nano-composites
Bio-renewable polymers and composites

8. Outline Plastics from vegetable oils (thermosets) Composites
Free radical polymerization
Cationic polymerization
Ring-opening metathesis polymerization
Composites
Polyurethane Coatings

9. U.S. Soybean Oil Production. Source: USDA
Advantages of Natural Oils
Readily available on a huge scale.
Very inexpensive.
Natural and renewable.
High purity.
Relatively high molecular weight.
Can be genetically engineered.
Many structurally related natural oils are readily available.
Million Metric Tons
Billion Pounds
U.S. Soybean Oil Production. Source: USDA

10. Soybean Oil Structure Oleic acid 22% Linoleic acid 54%
Linolenic acid 8%

11. Natural and Conjugated Oils
Oil C=C Bonds % Composition
Conjugated
No.
C18:1
C18:2
C18:3
Regular soy oil (SOY)
LoSatSoy oil (LSS) Conjugated LSS (CLS) Linseed oil (LIN) Conjugated linseed oil (CLIN) Tung oil (TUN) no
yes
4.5
5.1
5.8
8.2 22 20 19 5 54 64 15 7 8 9 57
85a
a -Eleostearic acid (9,11,13-octadecatrienoic acid) ?

12. Free Radical Polymerization

13. Free Radical Polymerization of Conjugated Soybean Oil
Sample Tg
(ºC)
Tan Delta
T10
T50
Tmax %
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
4.5
95.5
CLS70-AN27-DVB3-AIBN1 49
6.8
93.2
Sample Tg
(ºC)
Tan Delta
T10
T50
Tmax %
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

14. Cationic Polymerization

15. Mechanical Properties of Soybean Oil Polymers

16. Percentages of reacted oil
Polymers from Other Vegetable Oils
All oils have a triglyceride structure composed primarily of oleic acid, linoleic acid and linolenic acid.
Generally, higher unsaturation results in a plastic with higher mechanical properties.
Percentages of reacted oil

17. Polymers from Other Vegetable Oils
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.

18. Ring Opening Metathesis Polymerization of Oils
Dilulin
 Dilulin is found to have approximately 1 bicyclic unit per triglyceride.
 1H NMR and FTIR indicate the presence of norbornene-like hydrogens.

19. Ring Opening Metathesis Polymerization of Oils
Characteristics of Oil-Based ROMP Copolymers
Specimen Tg
(oC) υe
(mol/m3) E'
(MPa)
T10
T50
Tmax
% sol
Dil50-DCPD50 36
1377
228
427
461
462 21
Dil70-DCPD30 -9
1299
6.35
414
453 26
Dil90-DCPD10
-30
866
1.88
362
440
459 28
Dil100-DCPD0
-29
715 -
376
438
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

20. Ring Opening Metathesis Polymerization of Oils

21. Ring Opening Metathesis Polymerization of OilsTg
(oC) υe
(mol/m3)a
E’ at
25 oC (MPa)
NCO100
-17.1
318
2.4
NCO80NCA20
-6.2
740
5.7
NCO60NCA40
14.6
1664
27.8
NCO40NCA60
27.5
2790
130.0
NCO20NCA80
49.1
4418
583.4
NCA100
65.4
6028
831.9
Crosslink densities have been calculated at temperatures 50 oC above the Tg according to the equation:
An increase in the amount of NCA increases the Tg, the crosslink density, and the room temperature storage modulus

22. Outline Plastics from vegetable oils (thermosets) Composites
Free radical polymerization
Cationic polymerization
Ring-opening metathesis polymerization
Composites
Polyurethane Coatings

23. Soy-Glass Fiber Composites
Mechanical properties
Incorporating glass fiber
into the soy-based polymer results in good composites with improved properties.
Increasing crosslinking of
the polymer matrix can dramatically increase the mechanical properties.
 Fiber surface modification and compatibilization efforts are currently underway

24. Soy-Organomodified Clay Nanocomposites
Mechanical properties
1-2 wt % clay can significantly increase the mechanical properties.
CLS affords better mechanical properties than CSOY.

25. Linseed Oil-Natural Fiber Composites
Mechanical properties
CLIN-Kenaf Fiber
CLIN-Woodflour
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

26. Tung Oil-Spent Germ Biocomposites
Matrix: TUN50-BMA35-DVB15-TBPO Fillers: Spent Germ (~ 50 wt %)
Tensile test
Flexural test
Incorporating spent germ can significantly increase the mechanical properties
Particle size plays an important role in improving the materials performance

27. Corn Stover Biocomposites
Matrix: CSOY50-BMA35-DVB15-TBPO5
Filler: 2 mm Corn Stover
Matrix: (CSOY or CLIN)50-(BMA + DVB)50-TBPO5
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. 27

28. Wheat Straw Biocomposites
Matrix: CLIN50-BMA35-DVB15-TBPO5
Filler: 2 mm Wheat Straw
Matrix: (CLIN)50-(BMA + MA)35-DVB15-TBPO5
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. 28

29. Outline Plastics from vegetable oils (thermosets) Composites
Free radical polymerization
Cationic polymerization
Ring-opening metathesis polymerization
Composites
Polyurethane Coatings

30. Vegetable Oil-Based Dispersions

31. Vegetable Oil-Based Dispersions
(4.0)
(2.8)
(2.4)

32. Vegetable Oil-Based Dispersions
The Tg of the SPU films increases
linearly with an increase in the OH
functionality.
The mechanical properties of the
SPU films increase with the OH
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.

33. Vegetable Oil-Based Cationic PU Dispersions

34. Vegetable Oil-Based Cationic PU Dispersions2 3 4 6 5
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.

35. 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.

36. Questions?/Discussion

37. Extra Slide 1 Conjugation of Natural Oils Oil % Conjugation Linseed
Walnut
Safflower
Sunflower
Soy
Corn
Sesame
Peanut
% Conjugation
100 85 91 82 78 74 70
J. Am. Oil. Chem. Soc. 78, 447 (2001)

38. Damping Properties of Soybean Oil Polymers