Progress 09/01/08 to 08/31/12
Outputs
OUTPUTS: The objective was to develop a new family of biobased, biodegradable monomers and to study the effect of the material structure on the end properties. The focus was on segmented thermoplastic elastomers consisting of the hard and soft blocks. Activities were preparation of a variety of acid methyl esters by transesterification, epoxidation, hydrogenation, hydroformylation, and ozonolysis; Preparation of polyester diols by transesterification of a variety of glycols and hydroformylated fatty acids; Preparation of polyurethanes from diols of the previous step having soft segment concentration and testing the resulting properties; Preparation of polyureas-urethane using the previous products and testing the properties; Ozonolysis of vegetable oils and preparation of methyl esters of hydroxynonanoic acid; Preparation and property testing of segmented polyamide-polyesters and polyester elastomers using transesterification of polylactic acid with diacids and esterification of hard block polyesters with polyester diols. Characterization of monomers and intermediary products (diols) involved wet analysis, FTIR, NMR, GC/MC, HPLC and GPC, DSC and XRD. Characterization of polymers included FTIR, NMR, XRD, and electron microscopy, molecular weight measurements: DSC, DMA, TMA, DEA, TGA; tensile tests and processing (injection molding and extrusion). All testing and analysis was carried out under procedures outlined in the appropriate ASTM protocols. Detailed study of structure and properties of selected new materials was carried out jointly with Argonne National Lab (small-angle X-ray scattering, SAXS) and Bruker, Nano Surfaces Business (atomic force microscopy, AFM). In the last year, work was done to improve TPU8 (from ethoxylated methylricinoleate, and TPU9 (from ethoxylated 9-hydroxynonanoate. The work involved preparation of monomers and their characterization. Special emphasis was put on purification of monomers since their quality affected molecular weight of polymers. New polyamide-ester elastomer (MW(HS) = 600) were prepared and characterized. This project's work with segmented polyurethanes led to a project on elastomers from isosorbide with Honeywell (Kansas City, MO). Galata Chemicals (Southbury, CT) manufactures a range of chemicals including epoxidized soybean oil. We have also supplied memory-shape elastomers created under this project to the Center for Innovation for Biomaterials in Orthopedic Research (CIBOR) at Wichita State University. The results and progress were presented each year at the ACS & AOCS Annual Meetings, Polyurethanes Technical Conferences, BioEnvironmental Polymer Society Conference and other International conferences. Other constituents that received information: KS Dept of Commerce, KS Bioscience Authority, the Governor's office, visiting dignitaries, local high school students, and PSU Plastic Engineering students. Industrial partners include Honeywell Federal Manufacturing & Technologies, LLC, and Galata Chemicals. PARTICIPANTS: Zoran Petrovic, P.I. Directed research, reviews results, planning experiments. Ivan Javni, Senior Associate, Performed hydroformylation of oleic acid, polymerization of the product to polyols and preparation and testing of polyurethane elastomers. Mihail Ionescu, Senior Associate, Preparation of new monomers by ethoxylation of hydroxy fatty acids. Yijin Xu, Senior Associate, synthesis of ricinoleic polyols and polyurethanes, testing properties and analyzing the results. Omprakash Yemul, Post Doc Assoc, Synthesis of polyols from hydrogenated ricinoleic acid, preparation of polyurethanes and testing properties. Kamal Aly, Post Doc Assoc, Preparation of monomers by co-metathesis of oils with ethylene; selective hydrogenation to increase oleic acid content in oils. Ivana Cvetkovic, Research Associate, Preparation of polymers ethoxylated hydroxy fatty acids, preparation of monomers by ozonolysis. Jelena Milic, Research Associate, Ozonolysis of oils to make 9-hydroxy nonanoic acid, polymerize to polyesters, make polyurethanes with soft segments from 9-hydroxy nonanoic acid, polyamides. Min Liu, Graduate Student, Assisted Senior Associate in synthesis of ricinoleic polyols and polyurethanes, testing properties Qiang Luo, Post Doc Assoc, Prepared vinylated oils, polymerized them and tested properties. Olivera Bilic, Graduate Student, Assisted Senior Associate in preparation of new monomers, testing properties. Nikola Bilic, Graduate Student, Assisted Post doc in preparation of vinylated oils, testing properties. Jie Lin, Undergraduate student, Assisted Senior Associate with mechanical testing and thermal characterization. Karthik Venkatshan, Post Doc Assoc, Dielectric analysis of elastomers. Jeremy Donahue, Undergraduate student, Assisted Research Associate in casting samples from polyurethanes. Darko Ljubic, Graduate Student, assisted in studying effect of nano fillers on properties of polyurethane composites, participated in casting and testing of polyurethane elastomers. Dragana Radojcic, Graduate Student, assisted in the synthesis and testing of bio-degradable polyols and polyurethanes, prepared cast elastomers and foams. Her master thesis covers the topic of bio-based elastomers. Partner Organization: Ivan Ristic, PhD student, University of Novi Sad, Serbia, working with Senior Associate on polyester hard segments and polyurethanes. TARGET AUDIENCES: While the KPRC is primarily a research-focused institution, we participate in an ongoing effort at PSU and beyond to educate our constituents in the areas of polymer science, bio-based technologies, and the utilization of chemical research as an instrument of economic development. Through the course of this project, we shared the general scope and descriptions of this effort with high school groups (including Pittsburg High School, St. Mary's High School, and Baxter Springs High School), college undergraduate and graduate students and faculty (from PSU's Plastics Technology and chemistry departments), and a high school science teacher's group. Presentations were made throughout our region to the Kansas Department of Commerce, the Kansas Bioscience Authority, the Kansas Technology Enterprise Corporation, Southeast Kansas, Inc., and the Southeast Kansas Education Service Center at Greenbush. We maintain communication efforts with our partners in the Kansas state government, and shared parts of this project with local elected officials and the Governor's office. Other visiting constituents to KPRC during the past year included visiting alumni and campus dignitaries, visitors from Kazakstan, South Korea, and Mexico; and many industrial contacts. PROJECT MODIFICATIONS: This project was extended for one year under a no-cost extension.
Impacts
During the duration of this project, nine groups of thermoplastic polyurethane elastomers were developed and completely characterized. By varying the structure and concentration of soft and hard segments we obtained broad range of products with various properties (from very hard to very elastic materials) for different applications. The value of these thermoplastic elastomers is in their excellent processability by common methods used in thermoplastic processing such as injection molding, extrusion, thermoforming, blow molding, solution casting, and fiber spinning. They are also partially biodegradable and may be bio-compatible, suitable for some in-body medical applications (tubing, scaffolding, memory shape materials). A novel polyester- poly(hydroxynonanoic acid) was developed and fibers from this polyester have potential application as sutures and as biodegradable fabrics. Non-medical applications include shoe soles, elastomeric parts requiring some biodegradability, plasticizers for PVC and general applications where petrochemical TPU's are used. A patent application on technology for preparation bio-based thermoplastic polyurethanes is being prepared.
Publications
- Javni, I., Upshaw, T., Ljubic, D., Bilic, O., Wan, X., and Petrovic, Z.S., Sept 2012. Poster, Thermoplastic Polyurethane Elastomers With Mixed DI(2-Hydroxyethyl) Disulfide-1,4-butanediol Hard Segment, Polyurethanes Technical Conference, Atlanta, GA.
- Ljubic, D., Eastwood, E., Javni, I., Bilic, O., Petrovic, Z.S., and Ionescu, M., Sept 2012. Poster, Thermal and Thermo Oxidative Degradation Studies of Isosorbide Based Thermoplastic Polyurethane Elastomers", BioEnvironmental Polymer Society, Denton, TX.
- Petrovic, Z.S., Hong, D.P., Javni, I., Erina, N., Fan, Z., and Ilavsky, J., 2012. Phase structure in segmented polyurethanes having fatty acid-based soft segments, Polymer, pending.
- Javni, I., Hong, D., and Petrovic, Z.S., 2012. Polyurethanes from Soybean Oil, Aromatic And Cycloaliphatic Diamines By Non-Isocyanate Route, J Appl.Polym.Sci, accepted.
- Petrovic, Z.S., and Cvetkovic, I., 2012. Vegetable oil-based hyperbranched polyols in flexible foams, Contemporary Materials, III-1 (2012), 63-71.
- Petrovic, Z.S., Cvetkovic, I., Milic, J., Hong, D., and Javni, I., 2012. Hyperbranched polyols from hydroformylated methyl soyate, J Appl.Polym.Sci, 125(4), 2920-2928.
- Ionescu Mihail and Petrovic, Z.S., 2011. Polymerization of Soybean Oil with Superacids, Soybean Applications and Technology, Tzi-Bun Ng (Ed.), ISBN: 978-953-307-207-4.
- Javni, I., Bilic, O., and Petrovic, Z.S., Sept 2012. Poster, Bio-based Non-Isocyanate Polyurethanes, 103rd AOCS Annual Meeting & Expo, Long Beach, CA.
- Ljubic, D., Petrovic, Z.S., Srinivasan, M., and Javni, I., Sept 2012. Poster, Mechanical Properties of Functionalized Graphene Sheets/Polyurethane Nanocomposite Elastomers, Polyurethanes Technical Conference, Atlanta GA.
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Progress 09/01/10 to 08/31/11
Outputs
OUTPUTS: The objective of this project was to develop new thermoplastic biodegradable rubbers and elastomers from vegetable oils. The thermoplastic polyurethanes (TPU) developed in this project can be processed by standard techniques for thermoplastics such as injection molding, extrusion, thermoforming, blow molding and solution casting. They are also partially biodegradable and may be bio-compatible, suitable for some in-body medical applications (tubing, scaffolding, memory shape materials etc). Non-medical applications include shoe soles, elastomeric parts requiring some biodegradability, plasticizers for PVC and general applications where petrochemical TPU's are used. In order to achieve the project objectives it was necessary to develop new vegetable oil-based raw materials (monomers) and develop technologies for their conversion to final products (polymerization and processing). New monomers included ethoxylated 9-hydroxynonaoate and ethoxylated methylricinoleate. These were used to prepare polymer diols of molecular weight 2000 and segmented polyurethanes having varying soft segment concentrations. One of these thermoplastic polyurethanes is being tested in blends with PVC as a plasticizer. KPRC has nearly completed all planned work on this project resulting in new families of polyurethane elastomers. Detailed studies of structure and properties of some of new materials were carried out jointly with Dr. Jan Ilavsky of Argonne National Labs (Argonne, IL). Dr. Ilavsky's research group uses small-angle X-ray scattering (SAXS) from Argonne's Advanced Photon Source as a powerful tool for characterization of polymer systems. We also collaborated with the Nano Surfaces Business of Bruker (Santa Barbara, CA) to use atomic force microscopy to characterize our materials. This work should be published soon. The results and progress on this project have been shared with a variety of local and national constituents. Oral and poster communications were presented at the Northeastern Oklahoma Pentasectional ACS Meeting in Bartlesville, OK (March 2011) and the 102nd AOCS Annual Meeting & Expo in Cincinnati, OH (May 2011). Industrial partners for this project include Honeywell Federal Manufacturing & Technologies and Galata Chemicals. This project's work with segmented polyurethanes led to a project on elastomers from isosorbide with Honeywell (Kansas City, MO). Galata Chemicals (Southbury, CT) manufactures a range of chemicals including epoxidized soybean oil. We have also supplied memory-shape elastomers created under this project to the Center for Innovation for Biomaterials in Orthopaedic Research (CIBOR) at Wichita State University. Kansas constituents that received information about this effort include the Kansas Department of Commerce, the Kansas Bioscience Authority, the Kansas Technology Enterprise Corporation, and the Governor's office. Knowledge and general project updates are shared with visitors to PSU and the KPRC and include high school groups, plastics students and alumni, elected officials, and visiting dignitaries from industry and international partners. PARTICIPANTS: Zoran Petrovic, P.I. Directed research, review results, planning experiments. Ivan Javni, Senior Associate, Performed hydroformylation of oleic acid, polymerization of the product to polyols and preparation and testing of polyurethene elastomers. Mihail Ionescu, Senior Associate, Preparation of new monomers by ethoxylation of hydroxy fatty acids. Karthik Venkatshan, Post Doc Assoc, Dielectric analysis of elastomers. Kamal Aly, Post Doc Assoc, Peparation of monomers by co-metathesis of oils with ethylene; selective hydrogenation to increase oleic acid content in oils. Ivana Cvetkovic, Research Associate, Peparation of polymers ethoxylated hydroxy fatty acids, preparation of monomers by ozonolysis and hyperbranched polyols. Olivera Bilic, Graduate Student, Assisted Senior Associate in preparation of new monomers, testing properties. Nikola Bilic, Graduate Student, Assisted Post doc in preparation of vinilated oils, testing properties. Jeremy Donahue, Undergraduate student, Assisted Research Associate in casting samples from polyurethanes. TARGET AUDIENCES: While the KPRC is primarily a research-focused institution, we participate in an ongoing effort at PSU and beyond to educate our constituents in the areas of polymer science, bio-based technologies, and the utilization of chemical research as an instrument of economic development. Through the course of this project, we shared the general scope and descriptions of this effort with high school groups (including Pittsburg High School, St. Mary's High School, and Baxter Springs High School), college undergraduate and graduate students and faculty (from PSU's Plastics Technology and chemistry departments), and a high school science teacher's group. Presentations were made throughout our region to the Kansas Department of Commerce, the Kansas Bioscience Authority, the Kansas Technology Enterprise Corporation, Southeast Kansas, Inc., and the Southeast Kansas Education Service Center - Greenbush. We maintain communication efforts with our partners in the Kansas state government, and shared parts of this project with local elected officials and the Governor's office. Other visiting constituents to KPRC during the past year included visiting alumni and campus dignitaries, visitors from Kazakstan, South Korea, and Mexico; and many industrial contacts. PROJECT MODIFICATIONS: This project was extended for one year under a no-cost extension. We anticipate finishing the project by August 31, 2012.
Impacts
Novel thermoplastic polyurethanes with high bio-based content (30-90%) were prepared from hydroxy fatty acids (HFA) or their methyl esters, diisocyanates and short chain diols (chain extenders). Diisocyanates are of petrochemical origin but other resin components could be from renewable resources (either ours or from a commercial source). Diisocyanate in this work was diphenylmethane diisocyanate and CE was butane diol. HFA were obtained from vegetable oils. Hydroxy fatty acids and their methyl esters can be polymerized to high molecular weight polyesters of commercial value. However, their molecular weight is limited to several hundred to 6,000 for application in polyurethanes. These oligomers must have terminal OH groups i.e., they are diols. Typical mono hydroxy fatty acids can be in the acid form or preferably in the form of methyl esters (ethyl and higher esters are also possible but of lower economic value). Ones used in this work included ricinoleic acid, epoxidized and hydrogenated oleic acid, 9-hydroxynonanoic acid and many of their derivatives. Hydroxy fatty acids are polymerized from a diol, typically hexane diol or diethylene glycol to obtain a polyol of the desired molecular weight (1000-4000). Molecular weight is controlled by the ratio of hydroxyacid/diol. The polyol is then reacted with the excess of isocyanate to obtain a prepolymer which with a chain extender gives high molecular weight thermoplastic urethane. Several groups of polyurethanes were prepared including those with soft segments from methyl ricinoleate diols and derivatives, oleic acid methyl esters with primary and secondary OH groups, polyurethanes from PHNA diols having soft segment concentrations from 50-80%; and other combinations. Especially promising were thermoplastic polyurethanes from oleic acid methyl esters (prepared by hydroformylation) which showed very high mechanical properties. The other promising group was the PHNA diols, which displayed memory shape effects. The emphasis in the last year was on ethoxylated hydroxy acids. These included the synthesis, formation, and characterization of TPU's from ethoxylated methylricinoleate diol with MW = 2,000 g/mol; Ethoxylation of 9-hydroxynonaoate and the resulting polyurethanes and TPU's.
Publications
- Mihail Ionescu, Xianmei Wan and Zoran S. Petrovic, Dec 2010. Cashew Nut Oil Polyols For Polyurethanes, International Chemical Congress of Pacific Basin Societies-PACIFICHEM 2010, Honolulu, Hawaii.
- J. Hong, D. DeGruson, D. P. Hong, I. Javni, Z. S. Petrovic, Mar 2011. Reactions of Model Internal Epoxides with Carbon Dioxide. 56th Annual Pentasectional ACS Meeting, Bartlesville, OK.
- Q. Luo, M. Ionescu, Z. S. Petrovic, Mar 2011. Thermosetting Allyl Resins Derived from Fatty Acids, 56th Annual Pentasectional ACS Meeting, Bartlesville, OK.
- D. Hong, I. Javni, Z. S. Petrovic, Mar 2011. Polyols and Polyurethanes from Hydroformylated Corn Oil, 56th Annual Pentasectional ACS Meeting, Bartlesville, OK.
- I. Javni, D. P. Hong, M. Ionescu, Z. S. Petrovic, Mar 2011. Glycerin Based Rigid PU foams: Challenges and Solutions, 56th Annual Pentasectional ACS Meeting, Bartlesville, OK.
- M. Ionescu, X. Wan, Z. S. Petrovic, Mar 2011. Sulfur-Containing Polyols for Flexible Polyurethane Foams, 56th Annual Pentasectional ACS Meeting, Bartlesville, OK.
- J. Milic, I. Cvetkovic , Z. S. Petrovic Mar 2011. Application of Multiangle Light Scattering Analysis for the Characterization of Hyperbranched Polyol56th Annual Pentasectional ACS Meeting, Bartlesville, OK.
- Z.S. Petrovic, I. Javni, O. Bilic, Mar 2011. Improving Hardness of Flexible Polyurethane Foams with Nanofillers, 56th Annual Pentasectional ACS Meeting, Bartlesville, OK.
- Changhong Zhang, Zoran Petrovic, Mar 2011. Preparation of triglycerides with terminal double bonds by cometathesis of soybean oil with ethylene, 56th Annual Pentasectional ACS Meeting, Bartlesville, OK.
- I. Javni, Z. Petrovic, Apr 2011. Soy bean-based polyurethane by non-isoycanate route, United Soybean Association (USB), Technical Advisory Panel, Detroit, Mich.
- Z. Petrovic, James R. Halladay, Apr 2011. Soybean oil plasticizers as replacement of petroleum oil in rubber, United Soybean Association (USB), Technical Advisory Panel, Detroit, Mich.
- Z.S. Petrovic, J. Hong, Q. Luo, M. Ionescu and B. K. Shah, May 2011. Properties of vegetable oil-based casting compounds prepared via click chemistry, 102nd AOCS Annual Meeting & Expo, Cincinnati, OH.
- I. Javni, O. Bilic, D-P Hong, Z.S. Petrovic, May 2011. The Effect of Nano and Micro Clay Fillers in Bio-based Thermoplastic Polyurethanes, 102nd AOCS Annual Meeting & Expo, Cincinnati, OH.
- I. Javni, O. Bilic, Z.S. Petrovic, May 2011. Characteristics of Some Algal Oils Useful for Industrial Applications, 102nd AOCS Annual Meeting & Expo, Cincinnati, OH.
- Mihail Ionescu, Ye Ji, William M. Shirley and Zoran S. Petrovic, 2011. Polyurethanes from hybrid vegetable oil-petrochemical polyester polyols, Chapter 5 in Renewable and Sustainable Polymers, Gregory F. Payne, Patrick B. Smith, eds., ACS symposium series vol. 1063 Washington, DC, pp.73-93. Omprakash S. Yemul and Zoran S. Petrovic, 2010. Novel Thermoplastic Polyurethane Elastomers based on Methyl-12-Hydroxy Stearate, Chapter 2 in Contemporary Science of Polymeric Materials- Editor(s): Ljiljana Korugic-Karasz, ACS symposium series vol. 1061, pp.29-39.
- Zoran S. Petrovic, Ivana Cvetkovic, 2011. Vegetable oil-based hyperbranched polyols in flexible foams, Contemporary Materials, (accepted).
- Zoran S. Petrovic, Ivana Cvetkovic, Jelena Milic, 2011. DooPyo Hong and Ivan Javni, Hyperbranched polyols from hydroformylated methyl soyate, J Appl.Polym.Sci, (accepted).
- Ivan Javni, Kevin Song, Jie Lin and Zoran S Petrovic, 2011. Structure and properties of flexible polyurethane foams with nano- and micro-fillers, Journal of Cellular Plastics, 47(4) 357-372.
- Zoran S. Petrovic, Yijin Xu, Jelena Milic, Gregory Glenn and Artur Klamczynski, 2010. Biodegradation of Thermoplastic Polyurethanes from Vegetable Oils, J. Polym.Environment, 18(2), 94-97.
- Mihail Ionescu, Zoran Petrovic and Xianmei Wan, 2010. Ethoxylated Soybean Polyols for Polyurethanes, J.Polym. Environment, 18:1-7.
- M. Ionescu, X. Wan and Z.S. Petrovic, 2010. Cashew nut oil polyols for polyurethanes, Polyurethanes 2010 Technical Conference, Houston, TX.
- I. Javni, S. Fu, D-P. Hong, O. Bilic, Oct 2010. Mihail Ionescu and Zoran S. Petrovic, Self-extinguishing glycerin-based polyurethane rigid foams, Polyurethanes 2010 Technical Conference, Houston, Texas.
- Kamal Aly, D. Degruson, Z. Petrovic, Oct 2010. Co-metathesis of methyl oleate and ethylene using homogeneous catalysts, ACS-45th Midwest Regional Meeting, Wichita, KS.
- J. Milic, Z.S. Petrovic, Oct 2010. Solution Properties of biobased hyperbranched polymers investigated by multiple detection size exclusion chromatography, ACS-45th Midwest Regional Meeting, Wichita, KS.
- D. Degruson, I. Cvetkovic, Z.S. Petrovic, Oct 2010. Chromatographic characterization of methylated hydroformylated soybean oil, ACS-45th Midwest Regional Meeting, Wichita, KS.
- Q. Luo, Z. Petrovic, Soybean-based thermoset resins, Oct 2010. ACS-45th Midwest Regional Meeting, Wichita, KS.
- M. Ionescu, X. Wan, Z. S. Petrovic, May 2011. Considerations on the Mechanism of Self-Condensation of Glycerol to Polyglycerol in Presence of Alkaline Catalysts, 102nd AOCS Annual Meeting & Expo, Cincinnati, OH.
- Jian Hong, Doo Pyo Hong, Ivan Javni, Zoran S. Petrovic, May 2011. Model Reaction for Vegetable Oil-based Polyurethane by Nonisocyanate Route, 102nd AOCS Annual Meeting & Expo, Cincinnati, OH.
- Z. S. Petrovic and Omprakash Yemul, Jun 2011. Thermoplastic Elastomers from Modified Oleic Acid, World Conference on Oilseed Processing, Fatts & Oil Processing, Biofuels &Applications, Izmir, Turkey.
- Zoran S. Petrovic, Ivana Cvetkovic, Jul 2011. Polyurethane networks from renewable hyperbranched polyols, International Scientific Conference Contemporary Materials 2011, Banja Luka, Bosnia and Hercegovina.
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Progress 09/01/09 to 08/31/10
Outputs
OUTPUTS: In order to achieve the objective it was necessary to develop new vegetable oil-based raw materials (monomers) and develop technology for their conversion to final products (polymerization and processing). The second year plan was to investigate the feasibility of preparation of non-urethane elastomers such as polyesters and polyamids. The following tasks were performed: 1. Preparation of polylactic acid hard segment blocks of different molecular weights having terminal acid groups by transesterification of polylactic acid with diacids; 2. Preparation of polyester-polyester segmented elastomers by esterification of hard block polyester with polyester diols (the structure was selected from the results obtained in year one). To study the structure and properties of the polyester elastomers; 3. Preparation of polyamide hard segments of different molecular weights; 4. Preparation of polyamide-polyester segmented elastomers by esterification of hard block polyamie segments with polyester diols (the structure was selected from the results obtained in previous year); 5. To study the structure and properties of polyester-amide elastomers. Synthesis of polylactic acid hard segments of different chain length by polymerization of L-Lactide and DL-Lactide initiated by isosorbid. The following conferences were attended in which presentations or posters were presented: Am Chem Society 44th Midwest Regional Meeting, Iowa City, Iowa, Oct 2009; SAMPE, Fall Technical Conference & Exhibition, Wichita, KS, Oct 2009; Polyurethanes 2009 Technical Conference, Washington, D.C., Oct 2009; United Soybean Association (USB), Technical Advisory Panel, St Louis, MO, March, 2010; Am Chem Society Annual Meeting March 2010, San Francisco; Am Oil Chem Society Meeting May 2010, Phoenix. AZ; Contemporary Materials 2010, Banja Luka, Bosnia, July 2010. PARTICIPANTS: Zoran Petrovic, P.I. Directed research, review results, planning experiments. Ivan Javni, Senior Associate, Performed hydroformylation of oleic acid, polymerization of the product to polyols and preparation and testing of polyurethene elastomers. Mihail Ionescu, Senior Associate, Preparation of new monomers by ethoxylation of hydroxy fatty acids. Yijin Xu, Senior Associate, synthesis of ricinolec polyols and polyurethanes, testing properties and analyzing the results. Omprakash Yemul, Post Doc Assoc, Synthesis of polyols from hydrogenated ricinolec acid, preparation of polyurethanes and testing properties. Kamal Aly, Post Doc Assoc, Preparation of monomers by co-metathesis of oils with ethylene; selective hydrogenation to increase oleic acid content in oils. Ivana Cvetkovic, Research Associate, Preparation of polymers ethoxylated hydroxy fatty acids, preparation of monomers by ozonolysis. Jelena Milic, Research Associate, Ozonolysis of oils to make 9-hydroxy nonanoic acid, polymerize to polyesters, make polyurethanes with soft segments from 9-hydroxy nonanoic acid, polyamides. Qiang Luo, Post Doc Assoc, Prepared vinilated oils, polymerized them and tested properties. Olivera Bilic, Graduate Student, Assisted Senior Associate in preparation of new monomers, testing properties. Nikola Bilic, Graduate Student, Assisted Post doc in preparation of vinilated oils, testing properties. TARGET AUDIENCES: Nothing significant to report during this reporting period. PROJECT MODIFICATIONS: Nothing significant to report during this reporting period.
Impacts
The objective of this project is to develop new thermoplastic biodegradable rubbers from vegetable oils that can be injection molded and extruded. Our scientific objective is to develop a new family of flexible, bio-based, and biodegradable monomers and polymers that are useful for medical and athletic applications. Thermoplastic polyurethanes (TPU) can be processed by standard techniques for thermoplasts such as injection molding, extrusion, thermoforming, blow molding and solution casting. They are also partially biodegradable and may be bio-compatible, suitable for some in-body medical applications (tubing, scaffolding, memory shape materials etc). Non-medical applications may include shoe soles, different elastomeric parts requiring some biodegradability, and generally applications where petrochemical thermoplastic polyurethanes are used. The KPRC has successfully completed all planned work for year 2 on this project resulting in eight families of polyurethane elastomers. Some of these materials display excellent shape memory effect and are being assessed by a research group at Wichita State University and Via Christi Medical Center for biodegradability. Some polyester-ester and polymide-ester elastomers were developed but with inferior properties compared to polyurethane elastomers. This is mainly due to the difficulty of reaching high enough molecular weights. The work is still in progress but enhanced biodegradability of polylactic polyesters can be expected. The base raw material for elastomers is oleic acid which is commercially derived from high oleic oils, which are rather expensive. We have developed a method for selective hydrogenation of soybean and other inexpensive oils to maximize oleic acid content. A novel polyester- poly(hydroxynonanoic acid) was developed and the results published in Macromolecules. Fibers from this polyester have potential application as sutures and as biodegradable fabrics.
Publications
- Mihail Ionescu, S. Sinharoy and Zoran S. Petrovic, 2009. Polyacetal polyols for polyurethanes. J Polymer and Environment, 17, 123-130.
- Mihail Ionescu and Zoran S.Petrovic, 2010. High Functionality Polyether Polyols based on Polyglycerol. Journal of Cellular Plastics, Vol. 46(3), 223-237.
- M. Liu, Z. Petrovic, Y. Xu, 2009. Biobased Polyurethane Clay Nanocomposite Foams, Syntheses and Properties. Architecture Multifunctional Materials. Mtls Res Soc Symp, Vol 1188, Warrendale, PA.
- Zoran S. Petrovic, Ivana Cvetkovic, DooPyo Hong, Xianmei Wan, Wei Zhang, Timothy W. Abraham, Jeffrey Malsam, 2010. Vegetable Oil-Based Triols from Hydroformylated Fatty Acids and Polyurethane Elastomers. Eur. J. Lipid Sci. Technol., 112, pp 97-102.
- Zoran S. Petrovic, Jelena Milic, Yijin Xu and Ivana Cvetkovic, 2010. A chemical route to high molecular weight vegetable oil-based polyhydroxyalkanoate. Macromolecules, 43 (9) 4120-4125.
- Zoran S. Petrovic, Yijin Xu, Jelena Milic, Gregory Glenn and Artur Klamczynski, 2010. Biodegradation of Thermoplastic Polyurethanes from Vegetable Oils. J. Polym. Environment. Volume 18, Number 2, June 2010, 94-97.
- Mihail Ionescu, Zoran Petrovic and Xianmei Wan, 2010. Ethoxylated Soybean Polyls for Polyurethanes. J.Polym. Environment, 18:1-7.
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Progress 09/01/08 to 08/31/09
Outputs
OUTPUTS: The first year of work focused on segmented thermoplastic elastomers containing soft and hard domains. Seven groups of elastomers were developed and completely characterized by spectroscopic, thermal, dielectric and mechanical methods. Linear polyesters (polyalkanoates) from hydroxynonanoic acid: 9-Hydroxynonanoic acid prepared for Group 6 of thermoplastic polyurethanes (TPU) was utilized to prepare high molecular weight linear polyester. This 100% bio-based polymer exhibited high tendency for crystallization. The polymer is potentially bio-degradable and may be useful for medical use. This polymer was completely characterized and a paper was sent to Biomacromolecules. Characterization of the monomers and diols involved Infrared spectroscopy (FTIR), NMR, GC/MS, HPLC and GPC, DSC, wet analysis (OH number, acid number, iodine value) and X-ray diffraction (XRD). Characterization of polymers included FTIR, NMR, XRD, electron microscopy, molecular weight measurements (GPC, light scattering, vapor pressure analysis, dilute solution viscosity measurements), DSC, dynamic mechanical analysis (DMA), thermomechanical analysis (TMA), dielectric analysis (DEA), thermogravimetry (TGA), tensile tests and processing (injection molding and extrusion). All testing and analysis was carried out under procedures outlined in the appropriate ASTM protocols. The following conferences were attended in which presentations and posters were presented: Polyurethanes Technical Conference, San Antonio, Sept.29-Oct.1, 2008; Contemporary Science of Polymeric Materials, Feb 28 - March 2, 2009, Malta; 2nd Workshop on Fats and Oils as Renewable Feedstock for the Chemical Industry, Emded, Germany, March 22-24 2009;United Soybean Association (USB), Technical Advisory Panel, Detroit, Michigan, April 28-29, 2009; Bio-Environmental Polymers Society meeting, June 17-19, 2009, Chicago; YUCOMAT, Herceg Novi, August 30-Sept. 4, 2009. PARTICIPANTS: Zoran Petrovic, P.I. Directed research, review results, planning experiments. Ivan Javni, Senior Associate, Performed hydroformylation of oleic acid, polymerization of the product to polyols and preparation and testing of polyurethene elastomers. Mihail Ionescu, Senior Associate, Preparation of new monomers by ethoxylation of hydroxy fatty acids. Yijin Xu, Senior Associate, synthesis of ricinolec polyols and polyurethanes, testing properties and analyzing the results. Omprakash Yemul, Post Doc Assoc, Synthesis of polyols from hydrogenated ricinolec acid, preparation of polyurethanes and testing properties. Kamal Aly, Post Doc Assoc, Peparation of monomers by co-metathesis of oils with ethylene; selective hydrogenation to increase oleic acid content in oils. Ivana Cvetkovic, Research Associate, Peparation of polymers ethoxylated hydroxy fatty acids, preparation of monomers by ozonolysis. Jelena Milic, Research Associate, Ozonolysis of oils to make 9-hydroxy nonanoic acid, polymerize to polyesters, make polyurethanes with soft segments from 9-hydroxy nonanoic acid, polyamides. Min Liu, Graduate Student, Assisted Senior Associate in synthesis of ricinolec polyols and polyurethanes, testing properties Qiang Luo, Post Doc Assoc, Prepared vinilated oils, polymerized them and tested properties. Olivera Bilic, Graduate Student, Assisted Senior Associate in preparation of new monomers, testing properties. Nikola Bilic, Graduate Student, Assisted Post doc in preparation of vinilated oils, testing properties. Jie Lin, Undergraduate student, Assisted Senior Associate with mechanical testing and thermal characterization. Partner Organization: Ivan Ristic, PhD student, University of Novi Sad, Serbia, working with Senior Associate on polyester hard segments and polyurethanes. TARGET AUDIENCES: Nothing significant to report during this reporting period. PROJECT MODIFICATIONS: Nothing significant to report during this reporting period.
Impacts
KPRC has successfully completed all planned work for 2009 on this project and preparation of a patent application is in progress. We developed new monomers from vegetable oils and prepared thermoplastic polyurethane elastomers. All monomers were hydroxy fatty acid methyl esters derived from vegetable oils (primarily soybean and castor oils). These thermoplastic elastomers contained bio-based soft segments which give elasticity and petrochemical hard segments which act as physical crosslinks. In this work we examined different bio-based monomers to make polyester polyols, which were then reacted with isocyanate (MDI) and butane diol to produce polymers. By varying soft segment content (SSC) from 40-80%, we obtained elastomers of varying hardness and elasticity. Higher SSC values give higher bio-based content, higher elasticity and lower hardness. The value of thermoplastic polyurethane elastomers is in their excellent properties and processability by fast methods used in thermoplastic processing such as injection molding, extrusion, thermoforming etc. The global market for polyurethane elastomers (also called Thermoplastic Polyurethanes or TPU's) is estimated to about 1.5 million tons. TPU are higher value products compared to polyurethanes in foams (our previously primary application focus), and represent a valuable economic and scientific addition to KPRC's research portfolio.
Publications
- Zoran S Petrović and Jelena Milić, (2010). Thermoplastic polyurethane elastomers with high bio-based content, Ppaper sent to GPEC, Orlando. Omprakash S. Yemul and Zoran S. Petrović,(2009). Novel Thermoplastic Polyurethane Elastomers based on Methyl-12-Hydroxy Stearate, (A chapter in an ACS symposium book Contemporary Science of Polymeric Materials submitted).
- Zoran S. Petrović, Yijin Xu, Jelena Milić, (2010). Gregory Glenn and Artur Klamczynski, Biodegradation of Thermoplastic Polyurethanes from Vegetable Oils, (submitted to Journal of Polymers in the Environment).
- Zoran S. Petrović, Ivana Cvetković, DooPyo Hong, Xianmei Wan, Wei Zhang, Timothy W. Abraham, Jeffrey Malsam, (2009). Vegetable Oil-Based Triols from Hydroformylated Fatty Acids and Polyurethane Elastomers, European Journal of Lipid Science and Technology (accepted).
- Ivana Cvetković, Jelena Milić, Mihail Ionescu and Zoran S. Petrović,(2008). Preparation of 9-hydroxynonanoic acid methyl ester by ozonolysis of vegetable oils and its polycondensation, Hem. Ind. 62 (6), 319-328.
- Y. Xu, Z.S. Petrovic, S. Das, G. L. Wilkes, (2008). Morphology and Properties of Thermoplastic Polyurethanes with Dangling Chains in Ricinoleate-Based Soft segments, Polymer 2008, 49, 4248-4538.
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