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 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

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

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

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

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

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

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

Soybean Oil Structure 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) 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) ?

Free Radical Polymerization

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

Cationic Polymerization

Mechanical Properties of Soybean Oil Polymers

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

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.

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.

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

Ring Opening Metathesis Polymerization of Oils

Ring Opening Metathesis Polymerization of Oils Tg (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

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

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

Soy-Organomodified Clay Nanocomposites Mechanical properties 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 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 Incorporating spent germ can significantly increase the mechanical properties Particle size plays an important role in improving the materials performance

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

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

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

Vegetable Oil-Based Dispersions

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

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.

Vegetable Oil-Based Cationic PU Dispersions

Vegetable Oil-Based Cationic PU Dispersions 2 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.

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 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)

Damping Properties of Soybean Oil Polymers