Grantee Research Project Results
Final Report: Plant-Derived Materials to Enhance the Performance of Polyurethane Materials
EPA Grant Number: R831436Title: Plant-Derived Materials to Enhance the Performance of Polyurethane Materials
Investigators: Nelson, Chad , Hsu, Shaw Ling
Institution: University of Massachusetts - Amherst
EPA Project Officer: Richards, April
Project Period: January 5, 2004 through July 4, 2007
Project Amount: $350,000
RFA: Technology for a Sustainable Environment (2003) RFA Text | Recipients Lists
Research Category: Sustainable and Healthy Communities , Pollution Prevention/Sustainable Development
Objective:
This project encompasses two aspects of high performance materials involving the use of biomass (plant) feedstock. Although petroleum prices have fluctuated greatly in the last few years, it is our conviction that eventually plant-based materials need to be utilized as feedstocks for chemicals, monomers, and polymers. The cost of petroleum is no longer the ONLY issue. The fact is that refinery efficiency is very high at this moment. The percentage of liquid fuel continues to increase in percentage basis, so that many of the soft materials formerly synthesized from residuals are no longer available. In addition, the performance of these new plant-based materials is quite satisfactory. In our studies, we have developed polyurethane formulations with significant reductions of the most toxic component, isocyanate. Also, in conjunction with our industrial partners, we have developed new applications (commodity materials & high value biomedical devices) for biomass-based poly(lactic acid). We have also broadened the use of various plant oils in a number of applications requiring multi-functional crosslinkable polymers.Summary/Accomplishments (Outputs/Outcomes):
In some commercial formulations, isocyanate is used approximately 680 times more than is necessary. This is due to the presence of immiscible reactive mixtures. The mixing of the components utilized in these formulations cannot be easily controlled. For example, it is not recognized that poly(ethylene oxide), a commonly used polyether because of its ideal elastic characteristics, in water has a theta temperature at 32 °C transforming a water-miscible polymer to one that does not readily mix with water. For reactive blends including poly(ethylene oxide), such as polyurethane formulations, miscibility changes significantly from a relatively small rise in temperature. The additional isocyanate is used to control the phase behavior and ensure that reactions are carried out to completion. Thus, it is crucial that we understand the factors that govern the stability of various reactive blends involving plant-based polyols, which are inherently hydrophobic in nature. Phase behavior in this case is even more difficult to control.
In the last few years, we have carried out numerous studies illustrating how small changes in chemical structure, end groups, and molecular weight can all significantly influence the miscibility behavior of isocyanate-containing polyurethane formulations. We have developed experimental techniques (scattering and spectroscopy) to characterize phase boundaries and molecular origins of specific interactions of various components. In addition, we have developed and will continue to develop various simulation techniques to predict the overall phase behavior utilizing the experimental interaction parameters. Plant-based feedstock has a very different structure and miscibility behavior compared to petroleum-based polymers. Only if we can control the miscibility behavior can we develop new applications for this new class of materials. These accomplishments are summarized in the publications listed below.
The phase behavior of the PPG/PCL/Acrylic ternary system was found to be quite similar to the PPG/ poly(hexamethylene adipate)/Acrylic copolymer system. All three binary subsystems are partially miscible, producing a one-phase region in the ternary blends. The ratio of methylene to ester groups for poly(hexamethylene adipate) (PHMA) and poly(hexamethylene sebacate) (PHMA), poly(hexamethylene sebacate) (PHMS), and PCL repeat units are 5, 7, and 5, respectively, suggesting that the dipole density of the aliphatic polyester influenced the miscibility with the polyether. In contrast, this change in structure does not affect the miscibility with the acrylic component. The sensitivity of miscibility to the chemical structure of the polyester selected for formulation of polyurethane adhesives is illustrated.
Poly(lactic acid) cannot be used as a commodity plastic because of the high structural perfection and the high degree of crystallinity induced during processing. We have characterized the inherent structural rigidity and correlated the changes in chain conformation to the processing procedure used. We have identified the intermolecular forces which stabilize the crystalline units. In addition, we have been able to control the crystallization process brought on by other configurational changes. For example, the addition of D-isomer to an all L segment can improve the aging behavior of the polymer. The origin of the extraordinary stability of the stereocomplex of the D and L chains has also been understood.
Conclusions:
Future Activities:
Unfamiliarity with plant-based materials can be overcome. We have made significant progress in research, in terms of both control of miscibility and morphological development. Generally speaking, eventually the production of materials based on bi-products of petroleum refining will come to a halt. This has little to do with oil price. Refining petroleum into liquid fuel (diesel, jet fuel, or gasoline) is so efficient now that the bi-products will diminish significantly. There is no other viable route to various chemicals, monomers, and polymers. We believe that this area of research is necessary for the vitality of the U.S. and world economies. This is also the belief of our industrial partners. Deployment of these new materials requires an understanding of their physical characteristics. Simplistic direct replacement of the current petroleum-based chemicals and polymers is wasteful and detrimental to our environment.
Journal Articles on this Report : 14 Displayed | Download in RIS Format
Other project views: | All 14 publications | 14 publications in selected types | All 14 journal articles |
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Aou K, Kang S, Hsu SL. Morphological study on thermal shrinkage and dimensional stability associated with oriented poly(lactic acid). Macromolecules 2005;38(18):7730-7735. |
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Aou K, Hsu SL. Trichroic vibrational analysis on the α-form of poly(lactic acid) crystals using highly oriented fibers and spherulites. Macromolecules 2006;39(9):3337-3344. |
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Aou K, Hsu SL, Kleiner LW, Tang F-W. Roles of conformational and configurational defects on the physical aging of amorphous poly(lactic acid). Journal of Physical Chemistry B 2007;111(42):12322-12327. |
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Duffy DJ, Heintz AM, Stidham HD, Hsu SL, Suen W, Paul CW. The competitive influence of specific interactions and extent of reaction on the miscibility of ternary reactive polymer blends: model for polyurethane adhesives. International Journal of Adhesion and Adhesives 2005;25(1):39-46. |
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Hashida T, Jeong YG, Hua Y, Hsu SL, Paul CW. Spectroscopic study on morphology evolution in polymer blends. Macromolecules 2005;38(7):2876-2882. |
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Heintz AM, Duffy DJ, Nelson CM, Hua Y, Hsu SL, Suen W, Paul CW. A spectroscopic analysis of the phase evolution in polyurethane foams. Macromolecules 2005;38(22):9192-9199. |
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Jeong YG, Hashida T, Hsu SL, Paul CW. Factors influencing curing behavior in phase-separated structures. Macromolecules 2005;38(7):2889-2896. |
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Jeong YG, Hashida T, Nelson CM, Hsu SL, Paul CW. Morphology evolution and associated curing kinetics in reactive blends. International Journal of Adhesion and Adhesives 2006;26(8):600-608. |
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Jeong YG, Ramalingam S, Archer J, Hsu SL, Paul CW. Influence of copolymer configuration on the phase behavior of ternary blends. Journal of Physical Chemistry B 2006;110(6):2541-2548. |
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Jeong YG, Pagodina NV, Jiang C, Hsu SL, Paul CW. Effects of polyester-poor phase microstructures on viscosity development of polymer blends. Macromolecules 2006;39(14):4907-4913. |
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Jeong YG, Hashida T, Wu G, Hsu SL, Paul CW. Analysis of the multistep solidification process in polymer blends. Macromolecules 2006;39(1):274-280. |
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Pogodina NV, Jeong YG, Ramalingam S, Jiang C, Hsu SL, Paul CW. Crystallization-induced interconnected structure in semicrystallizable polyester/polyether binary blends. Macromolecules 2006;39(19):6672-6676. |
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Ren Z, Zeng X, Yang X, Ma D, Hsu SL. Molecular modeling of the H-bonds in polyurethane with multiple donors and acceptors. Polymer 2005;46(26):12337-12347. |
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Yang X, Kang S, Yang Y, Aou K, Hsu SL. Raman spectroscopic study of conformational changes in the amorphous phase of poly(lactic acid) during deformation. Polymer 2004;45(12):4241-4248. |
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Supplemental Keywords:
Soybean, sugarcane, stent, implants.
, RFA, Scientific Discipline, TREATMENT/CONTROL, Sustainable Industry/Business, Chemical Engineering, Sustainable Environment, Environmental Chemistry, Technology, Technology for Sustainable Environment, elastomers, clean technologies, green design, alternative materials, clean manufacturing, carcinogenicity, coatings, plant derived polyurethane
Progress and Final Reports:
Original AbstractThe perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Conclusions drawn by the principal investigators have not been reviewed by the Agency.