Source: PITTSBURG STATE UNIVERSITY submitted to NRP
DIRECT CONVERSION OF BIO-BASED OILS TO NEW MATERIALS
Sponsoring Institution
National Institute of Food and Agriculture
Project Status
COMPLETE
Funding Source
OTHER GRANTS
Reporting Frequency
Annual
Accession No.
0221264
Grant No.
2010-38924-20706
Cumulative Award Amt.
$1,872,000.00
Proposal No.
2010-01239
Multistate No.
(N/A)
Project Start Date
Sep 1, 2010
Project End Date
Aug 31, 2015
Grant Year
2010
Program Code
[BB-G]- Polymer Research, KS
Recipient Organization
PITTSBURG STATE UNIVERSITY
1501 S. JOPLIN STREET
PITTSBURG,KS 66762
Performing Department
Kansas Polymer Research Center
Non Technical Summary
This project will develop efficient and economic technologies to convert renewable, bio-based oils and fatty acids to new products. Specifically, we will develop direct reactions with the double bonds found in bio-based oils. The resulting materials will be used as polymeric materials and building blocks for large markets with specialty and commodity applications. Bio-based starting materials will include oils and acids derived from soybeans, algae, and other naturally occurring, renewable feedstocks. Product areas will include monomers, oligomers and polymers that could be used as specialty oils, lubricants, additives and coatings. Vegetable and other bio-based oils contain internal double bonds which are less reactive and not readily polymerizable. We will focus on transformations that convert these oils into products in a single step. Many bio-based oils require multiple steps and the formation of intermediate species to form polymers, and the techniques developed in this project will be more efficient, more economical, and less expensive to produce. We have identified several chemistries which allow the direct reactions of the double bonds in renewable oils, including cationic polymerization, hydrosilylation, metathesis, and addition of phenol. We will optimize these technologies for bio-based oils, which will lead to ways of using 100% vegetable oils or will copolymerize them with a range of monomers for tailoring specific properties. Structure-property characterization will allow the creation of new polymers and materials for different applications. The benefits from this project include: (1) a reduction in U.S. dependence upon foreign petroleum by replacing petroleum-based feedstocks for plastics with bio-based feedstocks, (2) the creation of new uses for renewable, U.S. agricultural commodities such as soybeans and algae, and (3) development of new, "green" materials that will compete in the marketplace. Feedstocks based on plant-based oils have the advantage of more stable agricultural prices, and consumption of these oleochemicals is estimated to be several hundred thousand tons per year. The project will be conducted by scientists at the Kansas Polymer Research Center (KPRC) at Pittsburg State University. KPRC is housed in the new Tyler Research Center on the PSU campus. This 22,000 square foot, state-of-the-art facility offers all of the synthetic, production, and testing capabilities needed for the project. KPRC is known throughout the world for its work in converting vegetable oils to polymers for use in industrial polyurethanes. The KPRC is a Kansas Technology Enterprise Corporation center of excellence.
Animal Health Component
80%
Research Effort Categories
Basic
20%
Applied
80%
Developmental
(N/A)
Classification

Knowledge Area (KA)Subject of Investigation (SOI)Field of Science (FOS)Percent
51118992000100%
Knowledge Area
511 - New and Improved Non-Food Products and Processes;

Subject Of Investigation
1899 - Oilseed and oil crops, general/other;

Field Of Science
2000 - Chemistry;
Goals / Objectives
The objective of this project is to develop new strategies for the efficient and economical transformation of bio-based oils to polymers and new materials. We will develop reactive mechanisms based on cationic polymerization, hydrosilylation, and methathesis. We will also pursue new products made through the addition of phenolic compounds to double bonds. Bio-based sources will include soybean oils, naturally occurring fatty acids, and oils isolated from heterotrophic algae. Application areas for bio-based polymers created through these methods will include coating resins and additives, polymers for electrical insulation, adhesives, high pressure compressor or lubricating oils, and modifiers for rubber or asphalt. Research Plan - Year 1 1.Study the kinetics and mechanism of model compounds - fatty acid methyl esters of oleic, linoleic and linolenic (linseed oil FA) - for cationic polymerization, hydrosilylation, methathesis, and the Friedel Crafts addition of phenol. 2.Characterize products by spectroscopic and molecular weight measurements 3.Prepare and characterize high molecular weight oils through cationic polymerization. 4.Prepare and study polyacids by hydrolysis of polymeric oils 5.Study metathesis with ethylene and vegetable oils using selected catalysts. 6.Assist AMI with literature reviews; identify suitable algae strains and growth conditions to generate promising algal oils for polymer development. Research Plan - Year 2 1.Continue to prepare and characterize high molecular weight oils prepared by cationic polymerization, hydrosilylation, methathesis, and addition of phenol 2.Study of reactions on polymeric oils (epoxidation, crosslinking with thiols, hydrolysis of oils to polyacids) and test in different applications 3.Copolymerize oils 4.Test the products in different applications and measure their propertes. 5.Study hydrosilylation of fatty acid compounds with terminal double bonds. 6.Examine influence of different silanes on hydrosilylation and product properties 7.Prepare of oils with terminal double bonds. 8.Co-metathesis of selected fatty acids to obtain diacids. 9.Co-metathesis of fatty acids with unsaturated diols and diacids to obtain polyols. 10.Study alkylation of phenol with different oils 11.Explore propoxylation and ethoxylation of phenolated oils 12.Purchase promising algal oils from AMI, characterize and identify most promising candidates Research Plan - Year 3 1.Transfer Year 1 and Year 2 lessons to new oil sources, specifically algal oils 2.Work with industrial partners to identify suitable technologies for industrial application and commercialization 3.Continue to prepare polymers, characterize and analyze products 4.Further development of products by metathesis as the most complex technology
Project Methods
Low temperature, cationic polymerization of oils in the presence of BF3 catalysts yields oligomeric oils. We have discovered that superacids may produce some useful polymeric oils, but the process is dependent on the type of oil and the composition of fatty acid. We have seen that a relatively small amount of double bonds are consumed, compared with thermally polymerized oils. The residual double bonds can be further used for crosslinking as in drying oils. These new oils are suitable for coatings, and they can be a good foundation for printing inks. Hydrosilylation is the reaction of silicon hydride species with unsaturated substrates in the presence of a suitable catalyst. The hydrosilylation reaction leads directly to the formation of thermally and hydrolytically stable carbon-silicon bonds, and can be catalyzed by transition metal complexes. They typically proceed to high conversion almost without formation of byproducts. This study will examine the feasibility of crosslinking fatty acid model compounds having single or two to three double bonds. The results will be compared with those obtained with fatty acids with terminal double bonds obtained by metathesis with ethylene. Olefin metathesis is a process of cutting double bonds and recombining the fragments into new compounds. An unsaturated compound in the presence of a metathesis catalyst is cleaved at the double bond and recombined randomly to give a mixture of double bond containing compounds. When two unsaturated compounds are mixed in the presence of a metathesis catalyst, double bonds are cleaved and recombined randomly to give a rich mixture of new compounds (co-metathesis). We will study the direct polymerization of oils by metathesis with selected economical catalysts and characterization of products, the preparation of new monomers with terminal double bonds, identify the best catalysts for these reactions, explore the development of new products by polymerization and copolymerization of oils with terminal double bonds, and prepare fatty acid diols and diacids by self-metathesis using appropriate catalysts. The introduction of aromatic groups to vegetable oils can add rigidity and strength. Bio-based oils with aromatic rings open a new area of chemistry and provide creative ways for modifying the structure for different properties and applications. Phenols can be reacted with formaldehyde to give methylol groups and allow creation of vegetable oil-based Mannich polyols for polyurethanes. Phenolated oils are also alkoxylated to obtain primary or secondary OH groups to serve as bio-based aromatic polyols for polyurethanes, or can be cured with aldehydes to obtain elastic phenolic resins. The phenol ring attached to vegetable oil can be used for further chemical transformations such as polycondensation reaction with carbonyl compounds to phenolic resins. Transformation of phenolic hydroxyl to new reactive groups (by alkylation, alkoxylation, esterification, condensation etc.) produces new polymeric structures.

Progress 09/01/10 to 08/31/15

Outputs
Target Audience:Target audiences were PSU Polymer Chemistry students, national and international scientific and industrial communities involved in technologies dealing with oils, polymers, adhesives, coatings and foams. Particularly useful were plastic symposia (ANTEC), AOCS meeting, United Soybean Technical Advisory Panel (TAP) meetings and Urethane Symposia and exhibitions. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided? Nothing Reported How have the results been disseminated to communities of interest?Through the course of this project, we shared the general scope and descriptions of this effort with high school groups, college undergraduate and graduate students, and faculty from PSU's Plastics Technology and chemistry departments. Presentations were made throughout our region to local civic groups, visiting constituents to PSU, alumni and campus dignitaries and many industrial contacts. 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. What do you plan to do during the next reporting period to accomplish the goals? Nothing Reported

Impacts
What was accomplished under these goals? The goal of the project was to convert vegetable oils directly to useful products or to develop methods that will use a minimal number of steps, to develop efficient and economic technologies to create new materials. Bio-based starting materials included oils and fatty acids derived from soybeans, algae, and other naturally occurring, renewable feedstocks. Product areas included monomers, oligomers and polymers that could be used as specialty oils, lubricants, additives, coatings and casting compounds for electrical other uses. Accomplishments for the duration of the project are as follows: Cationic polymerization of oils in the presence of fluoroboric acid at low temperature and room pressure was achieved. It was found that polymerized oils of different molecular weights and viscosity can be obtained. The mechanism of polymerization was elucidated and the samples of oils were tried as plasticizers in rubber. It has been shown that polymerized oils are a viable substitute for mineral oils and they are more economical and can copolymerize with rubber, making permanent (no leaching) additives. A chapter in a book was published and conference papers were presented. Detailed studies of cationic polymerization of fatty acids from soybean oil and model compounds-9-octadecene (OD), methyl oleate and methyl linoleate in presence of 1%, 5% and 10% of HBF4 showed complexity of the process. Methyl linoleate gave increased amount of oligomers with increasing catalyst concentration. Seven member ring formation was postulated and confirmed by NMR. The direct polymerizations of oils to obtain polymeric fatty acid were accomplished only with oils having high content of linoleic acids and were not efficient in high oleic oils. Alternative way of obtaining polyacids consisted in polymerizing epoxidized fatty acid methyl esters and converting ester groups to acids by saponification and acid treatment. Polyacids were used successfully to cure epoxidized soybean oil and diglycidylether of bisphenol A (commercial epoxy resins). Selective hydrogenation of soybean oil produced efficiently high oleic oils offering an inexpensive way to oleic acid as a source for different polymers or direct use in polyols by hydroformylation. Amine reaction with internal epoxies was investigated on epoxidized 9-octadecene as a model for oleic acid but without acid or ester group. It was found that the reaction does not proceed at 100; 170 and 200 oC without catalysts. The results were submitted for publication. The phenolation of vegetable oils was conducted. Phenol in the structure allows different reactions such as the preparation of polyols (by propoxylation, ethoxylation, Mannich reactions). The testing of new catalysts showed that alkylation of phenols was improved with fatty acids containing one double bond. Triflic acid catalyst is superior to HBF 4 for phenol alkylation with alkenes, but the latter gives a reasonable yield in alkylated products. Polyols were prepared and used for flexible polyurethane foams. Phenol alkylation using cashew nut liquid produced a number of excellent polyols and other chemical transformations. These polyols were used in rigid urethane foams of excellent quality. The work was published and reported at conferences. Co-metathesis of soybean oil with ethylene was investigated with the goal to make oils with terminal double bonds. Oils with terminal double bonds were prepared by metathesis or by reacting epoxidized oils with allyl alcohol. Metathesis was carried out with tungsten catalyst, as well as, Grubb's II catalyst. Tungsten catalysts were shown to produce good results at a lower price. Oils with terminal double bonds were copolymerized with maleic anhydride or crosslinked by hydrosilylation. Hydrosilylation of vegetable oils with internal double bonds proved not to be feasible under normal circumstances. Thus, derivatives of oils with terminal double bonds were used. Several technologies were used in the preparation of oils with terminal double bonds. These oils were used for crosslinking by hydrosilylation. Silicone-vegetable oils polymers were prepared by hydrosilylation of oils with terminal double bonds (allylated oils) but materials were relatively weak and not promising due to incompatibility of silicones with vegetable oils. Azide-alkyne cycloaddition using octadecene model compounds was utilized to produce crosslinked casting resins with triazine rings. This is a promising technology for preparing materials with increased thermal stability and potential semi-conductivity. A paper on the curing of azidated oils with short alkynes was published. Click chemistry reaction kinetics was studied on model compounds-allylated 9-octadecene and azidated 9-octadecene. Thermal curing kinetics of alkynated oils with azides with model compounds allowed assessment of the extent of reaction by GPC combined with spectroscopic methods. Results will help in designing a process for thermal polymerization of oil-based alkynes and azides. Direct conversion of a range of vegetable oils with mercaptoethanol was conducted with success. New polyols gave elastic casting resins except castor oil-mercaptoethanol products which gave glassy rigid polyurethanes and foams. The results were communicated at the 2014 AOCS meeting and a paper published. Reactions of mercaptanized soybean oil with a range of allyl organic compounds was utilized to prepare functionalized soybean oils with hydroxyl, amine, isocyanate, isothiocyanate, epoxy and silane terminal groups, useful for making new bio-based polymers. The work on thiol-ene was very successful and resulted in several publications and collaboration with our industrial partner. Not only new polyols were prepared with UV catalyzed thio-ene chemistry but also soy-based isocyanates, epoxides, silicones and amines were made and the results published. Thiol-ene reactions open the new area of materials based on functionalized oils with OH, amine, isocyanate and other functional groups which were not readily obtainable by alternative methods. The chemistry of algal oil was thoroughly investigated. The crude algal oil (AO) used in this work had low unsaturation, high content of free fatty acids and small amount of polyunsaturated fatty acids. Polyols were obtained from methanol ring-opened epoxidized AO which were used to make relatively good elastomers and rigid foams. Ozonolysis of algal oil was successfully carried out but the product (the polyol) had a lower OH number but gave some useful monomers. Polyols by hydroformylation of AO were very reactive and could be used for spray applications. The work on crude algal oil (AO) conversion to polyols and polyurethanes was completed and published. For the first time it was demonstrated that crude algal oil is viable raw material for many chemistries leading to useful products.

Publications

  • Type: Book Chapters Status: Published Year Published: 2014 Citation: Hong, Jian; Hairabedian, Djavan; Petrovic, Zoran; Myers, Andrew, "Polyacids from Corn Oil as Curing Agents for Epoxy Resins", a chapter in ACS Book: "Green Polymer Chemistry III: Biobased Materials and Biocatalysis" Manuscript ID: bk-2014-00614h.R1
  • Type: Journal Articles Status: Accepted Year Published: 2015 Citation: I Javni, O.Biic, D. Ljubic, X.Wan, Z.S. Petrovic and T.A. Upshaw, Polymercapatan-based polyurethane foams, J Cellular Plastics.
  • Type: Journal Articles Status: Published Year Published: 2015 Citation: Mihail Ionescu, Dragana Radojcic, Xianmei Wan, Zoran S Petrovic, Thomas A. Upshaw, Functionalized vegetable oils as precursors for polymers by thiol-ene reaction, Europ.Polym.J. 67 (2015) pp. 439-448; DOI information: 10.1016/j.eurpolymj.2014.12.037.
  • Type: Journal Articles Status: Published Year Published: 2015 Citation: Jian Hong, Dragana Radojcic, Djavan Hairabedian, Xianmei Wan, Zoran S Petrovic, Alkynated and azidated octadecane as model compounds for kinetic studies of Huisgen 1,3-dipolar cycloaddition in vegetable oils, Europ. J. Lipid Sci. TechnolArticle first publishes online:21 Jan 2015| DOI: 10.1002/ejlt.201400461.
  • Type: Journal Articles Status: Submitted Year Published: 2015 Citation: Dragana Radojcic, Jian Hong, Mihail Ionescu, Xianmei Wan, Ivan Javni and Zoran S. Petrovic, On The Reaction of Amines With Internal Epoxides, (submitted to J. Europ. Lipid Science).
  • Type: Journal Articles Status: Published Year Published: 2015 Citation: Vladislav Jaso, Gregory Glenn, Artur Klamczynski, Zoran S. Petrovic, Biodegradability Study of Polylactic Acid/Thermoplastic Polyurethane Blends, Polymer Testing, Volume 47, October 2015, Pages 13.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2014 Citation: ZS Petrovic, M Ionescu, D Radojcic and J Hong, Bio-Based Epoxy Resins,(plenary Lecture) 22nd Meeting of Bioenvironmental Polymer Society (BEPS), Kansas City, MO October 2014.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2014 Citation: O. Bilic, I. Javni, ZS Petrovic, Soybean oil-based non-isocyanate polyurethane adhesives, 22nd Meeting of Bioenvironmental Polymer Society (BEPS), Kansas City, MO, October 2014.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: M. Ionescu, D. Radojcic, X. Wan, Z. Petrovic and T. Upshaw, High functionality biobased polyols for rigid polyurethane foams, 106 AOCS Annual meeting, May 3-6, 2015, Orlando, Fl.


Progress 09/01/13 to 08/31/14

Outputs
Target Audience: Target audiences were PSU polymer chemical students, national and international scientific and industrial communities involved in technologies dealing with oils, polymers, adhesives, coatings and foams. Particularly useful were plastic symposiums (ANTEC), AOCS meeting, United Soybean Technical Advisory Panel (TAP) meetings and Urethane Symposium and exhibitions. Changes/Problems: This project has been granted an additional one-year no-cost extension. What opportunities for training and professional development has the project provided? Nothing Reported How have the results been disseminated to communities of interest? Through the course of this project, we shared the general scope and descriptions of this effort with high school groups, college undergraduate and graduate students, and faculty from PSU's Plastics Technology and chemistry departments. Presentations were made throughout our region to local civic groups, visiting constituents to PSU, alumni and campus dignitaries and many industrial contacts. 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. What do you plan to do during the next reporting period to accomplish the goals? Investigate sulfur chemistry- thiol-ene reactions for direct conversion of oils to new monomers and polymers; Perform silicone modification of oils to obtain novel moisture curable materials; Explore reactions of internal double bonds in oils with amines; Obtain novel polyols and polymers from high oleic acid by selective hydrogenation.

Impacts
What was accomplished under these goals? The goal of the project is to convert vegetable oils directly to useful products or to develop methods that will use a minimal number of steps to achieve this goal. This also means to develop efficient and economic technologies and create new materials. Ideally, oils should be reacted with an agent through double bonds and form a cross-linked product with good properties. Since internal double bonds are not reactive enough, oils with terminal double or triple bonds will be made and utilized as building blocks for large markets with specialty and commodity applications. Bio-based starting materials will include oils and acids derived from soybeans, algae, and other naturally occurring, renewable feedstocks. Product areas will include monomers, oligomers and polymers that could be used as specialty oils, lubricants, additives, coatings and casting compounds for electrical other uses. Accomplishments for the current year are the following: Direct polymerization of oils to obtain polymeric fatty acid were accomplished successfully only with oils having high content of linoleic acids and were not efficient in high oleic oils. Alternative way of obtaining polyacids consisted in polymerizing epoxidized fatty acid methyl esters and converting ester groups to acids by saponification and acid treatment. Polyacids were used successfully to cure epoxidized soybean oil and diglycidylether of bisphenol A (commercial epoxy resins). New program on preparing polyols by direct reaction of mercapto alcohols with vegetable oils was started which resulted in a range of polyols with different hydroxyl numbers. Cast resins and foams were made and properties examined. Thiol-ene reactions open the new area of materials based on functionalized oils with OH, amine, isocyanate and other functional groups which were not readily obtainable by alternative methods. This direction is very promising and will be pursued next year. Industrial partner is evaluating technology. Amine reaction with internal epoxies was investigated on epoxidized 9-octadecene- a model for oleic acid but without acid or ester group. It was found that the reaction does not proceed at 100; 170 and 200 oC without catalysts. The results were reported at AOCS Annual meeting and will be published. Further research on the topic will be in the plan for the next continuation. Silicone-vegetable oils polymers were prepared by hydrosilylation of oils with terminal double bonds (allylated oils) and the paper is being prepared for publication. Hydrosilylation as an alternative way of crosslinking oils can be used only in solutions due to incompatibility of components. “Click chemistry” reaction kinetics was studied on model compounds-allylated 9-octadecene and azidated 9-octadecene. Thermal curing kinetics of alkynated oils with azides was difficult to assess because the polymers were insoluble and spectroscopic methods were not adequate. Working with model compounds allowed easy assessment of the extent of reaction by GPC combined with spectroscopic methods. The results will help in designing process for thermal polymerization of oil-based alkynes and azides. Selective hydrogenation of soybean oil produced efficiently high oleic oils offering an inexpensive way to oleic acid as a source for different polymers or direct use in polyols by hydroformylation. Hydroformylation of high oleic oils produced polyols with primary hydroxyl groups and functionality similar to that of castor oil but no double bonds. Methanolysis of the polyol would give hydroxyl-fatty acid methyl esters useful for preparation of polyesters and polyester-urethanes as we proved before. Direct conversion of a range of vegetable oils with mercaptoethanol was conducted with remarkable success. New polyols were gave elastic casting resins except castor oil-mercaptoethanol products which gave glassy rigid polyurethanes and foams. Industrial partners were interested in new materials. The results were communicated at the 2014 AOCS meeting and the paper is in preparation. Reactions of mercaptanized soybean oil with a range of allyl organic compounds was utilized to prepare functionalized soybean oils with hydroxyl, amine, isocyanate, isothiocyanate, epoxy and silane terminal groups, useful for making new bio-based polymers,. Continuation of this work is proposed for the extension.

Publications

  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Omprakash Yemul and Zoran S. Petrovic, Thermoplastic polyurethane elastomers from modified oleic acid, Polymer International DOI:10.1002/pi.4771.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Vladislav Jaso, Miroslav Cvetinov, Srdan Rakic, Zoran S. Petrovic, Bioplastics and Elastomers from PLA/TPU Blends, J Applied Polym. Sci. 2014 DOI: 10.1002/app.41104.
  • Type: Journal Articles Status: Submitted Year Published: 2014 Citation: Vladislav Jaso, Marko V. Rodic, Zoran S. Petrovic, Biocompatible fibers from TPU reinforced with PLA microfibers.
  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Z. S Petrovic, I. Javni, M. Ionescu, Biological Oils as Precursors to Novel Polymeric Materials, Journal of Renewable Materials, Vol. 1, No. 3, July 2013, pp 167-186.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2014 Citation: Mihail Ionescu, Ram-krishna Gupta, Dragana Radojcic, Xianmei Wan, Zoran Petrovic, New Biobased Monomers from Limonene by Thiol-Ene Reactions, 105th Annual AOCS Meeting and Expo, San Antonio, TX, May 1-4, 2014.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2014 Citation: Z.S. Petrovic, M. Ionescu, D. Radojcic, On the Reaction of Internal Epoxy Groups with Amines, 105th Annual AOCS Meeting and Expo, San Antonio, TX, May 1-4, 2014.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: R. K. Gupta, M. Ionescu, D. Radojcic, X. Wan and Z. S. Petrovic, Novel Renewable Polyols Based on Limonene for Rigid Polyurethane Foams, J Polym Environ, 22:304-309; DOI 10.1007/s10924-014-0641-2.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2014 Citation: Zoran S. Petrovic, Commodity polymers from renewable resources, Atlantic Bio-Refinery Conference 2014 , Fields, Forests And Oceans: Building New Markets, June 4-7, Sidney, Nova Scotia, Canada.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2014 Citation: Zoran S Petrovic, Mihail Ionescu, Dragana Radojcic and Jian Hong, Advanced materials from corn: Isosorbide-based epoxy resins,(plenary lecture), International conference on Innovations in Energy, Polymer and Environmental Sciences, Satara, India, Jan 10-12, 2014.
  • Type: Journal Articles Status: Submitted Year Published: 2014 Citation: Alisa Zlatanic, Mihail Ionescu, Xianmei Wan and Zoran S. Petrovic, Polymer Networks From Vegetable Oils Crosslinked By Hydrosilylation.
  • Type: Journal Articles Status: Submitted Year Published: 2014 Citation: Mihail Ionescu, Dragana Radojcic, Xianmei Wan, Zoran S Petrovic, Monomers and Polymers by Thiol-ene Reactions of Vegetable Oils.
  • Type: Journal Articles Status: Submitted Year Published: 2014 Citation: Dragana Radojcic, Zoran S. Petrovic, Mihail Ionescu, Jian Hong, Xianmei Wan, Ivan Javni, On The Reaction Of Amines With Internal Epoxides.
  • Type: Journal Articles Status: Submitted Year Published: 2014 Citation: Jian Hong, Dragana Radojcic, Djavan Hairabedian, Xianmei Wan, Zoran S Petrovic, Kinetics of thermal reaction of model alkyne-azide compounds.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Vladislav Jaso, Gregory Glenn, Artur Klamczynski, Zoran S. Petrovic, Biodegradability Study of Polylactic Acid/Thermoplastic Polyurethane Blends, Journal of Polymers and Environment.


Progress 09/01/12 to 08/31/13

Outputs
Target Audience: Target audiences were national and international scientific and industrial communities involved in technologies dealing with oils, polymers, adhesives, coatings and foams, Particularly useful were plastic symposia (ANTEC), AOCS meeting, United Soybean Technical Advisory Panel (TAP) meetings and Urethane symposia and exhibitions. Changes/Problems: This project has been granted a one-year no-cost extension. What opportunities for training and professional development has the project provided? Nothing Reported How have the results been disseminated to communities of interest? The results were presented at American Chemical Society regional and national meetings, American Oil Chemists’ Society national conferences, United Soybean Board annual meeting and international conferences. Journal articles and symposia communications were published and presented with several being in preparation. The KPRC participates 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 locally the general scope and descriptions of this effort with high schools and colleges at Regional ACS meetings, college undergraduate and graduate students and faculty from PSU's Departments of Chemistry and Plastics Technology. 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, and many industrial contacts. What do you plan to do during the next reporting period to accomplish the goals? Continue direct polymerization of fatty acids using cationic initiators as an inexpensive way of making high molecular weight polymerized oils with special properties. They are intended for creation of polymeric fatty acids which will be used as gelling agents for oils. Metathesis will be used to create high olefins with internal double bonds suitable for studying model reactions of direct polymerization, epoxidation and formation of azides and alkynes, and investigate ring opening polymerization of model epoxides. Conversion of inexpensive vegetable oils to high value high oleic oils will be pursued with the aim of generating an inexpensive source of oleic acid necessary for the formation of polymers. Polyester polymers and prepolymers will be made from the hydroxy oleic acid or its methyl ester. The technology is geared towards high oleic acid oils using different though selective catalytic hydrogenation. Since selective hydrogenation in food science is geared towards low trans fats, they are not a concern in industrial applications. Thus, maximization of oleic acid or its isomers will be the ultimate goal. Properties of hydroformylated products will be tested in polyesters and polyurethanes.

Impacts
What was accomplished under these goals? The goal of the project is to convert vegetable oils directly to useful products or to develop methods that will use a minimal number of steps to achieve this goal. This also means to develop efficient and economic technologies and create new materials. Ideally, oils should be reacted with an agent through double bonds and form a crosslinked product with good properties. Since internal double bonds are not reactive enough, oils with terminal double or triple bonds will be made and utilized as building blocks for large markets with specialty and commodity applications. Bio-based starting materials will include oils and acids derived from soybeans, algae, and other naturally occurring, renewable feedstocks. Product areas will include monomers, oligomers and polymers that could be used as specialty oils, lubricants, additives, coatings and casting compounds for electrical other uses. Accomplishments for Year 3: Transfer Year 1 and Year 2 lessons to new oil sources, specifically algal oils. Results: the work on crude algal oil (AO) conversion to polyols and polyurethanes was completed and published. For the first time it was demonstrated that crude algal oil is viable raw material for many chemistries leading to useful products. Polyols by hydroformylation of algal oil were very reactive and could be used for spray applications. A paper was published and the results were reported at an international symposium. 2. Work with industrial partners to identify suitable technologies for industrial application and commercialization. Results: We talked with several industrial companies about various aspects or products developed in this project. These contacts include both existing and prospective partners, and application areas included new product development, new industrial processes, and improvements to current materials. Industrial contacts included an automotive OEM manufacturer, an agricultural materials producer, and an internationally-based chemical company interested in entering the bio-based feedstock industry. 3. To continue to prepare polymers, characterize and analyze products. Results: The plan for the third year of research included the following technologies: Hydrosilylation of vegetable oils with internal double bonds proved not to be feasible under normal circumstances. Thus, derivatives of oils with terminal double bonds were used. Crosslinked oils were prepared by reacting with five different silicon-hydride functionalized monomers and Karstedt’s catalyst. A molar ratio of silicon hydride to double bonds varied between 1 and 1.2. Due to poor compatibility, the oil and silicon compounds were cast from solution. Soft materials with glass transition from -50 to -5 oC were made. Networks from allylated oils containing cyclic tetramethylcyclotetrasiloxane swelled more than their counterparts prepared with branched Q resin in spite of shorter network chains. The best moisture resistance was observed in oil-based networks crosslinked with Q resin. Alkylation of phenol containing oils. In the previous study we alkylated phenols with different oils and fatty acids. Now we have used cashew nut liquid and developed a number of excellent polyols by alkylation and other chemical transformations. Polyols were used in rigid urethane foams of excellent quality. The work was published and reported at conferences. Detailed studies of cationic polymerization of fatty acids from soybean oil and model compounds-9-octadecene (OD), methyl oleate and methyl linoleate in presence of 1%, 5% and 10% of HBF4 showed complexity of the process.OD gave less than 8% of oligomers even at 10% of catalyst after 24 hours. However, in presence of methyl stearate the ester group is converted into carboxyl and reacted with double bond from OD (conversion ~ 16 %) giving estolide. Methyloleate polymerized with 1 and 5% HBF4 to a very low extent, probably through estolide formation, confirming that one double bond is not reactive in cationic polymerization. Methyl linoleate gave increased amount of oligomers with increasing catalyst concentration. Seven member ring formation was postulated and confirmed by NMR. Methyl linolenate polymerizes readily with high conversion. Preparation of oils with terminal double bonds using three technologies: 1) ring-opening of epoxidized soybean and linseed oils by allyl alcohol in the presence of superacid catalyst, followed by esterification of hydroxyls with acetic anhydride. Iodine value (IV) of these oils varied from 36 to 59%, Mn (by VPO) varied from 1400 to 2100, functionality 2 to 4.8 and viscosity 3.5-24 Pa s; 2) Ring-opening of epoxy groups of allyl glycidyl ether by hydroxyls of polyol from vegetable oils catalyzed by HBF4 and subsequent blocking of hydroxyls with acetic anhydride. IV varied from 67 to 79 %, Mn (VPO) was around 1900, f= 4.9 - 5.9 and viscosity 2-2.5 Pa s; 3) Reacting epoxidized soybean and linseed oils with 10-undecylenic acid in presence of amine catalysts such as benzimidazole, 2-ethyl-4methylimidazole, 4-dimethyl amino pyridine. It was found that the efficiency of the reaction of ring opening of epoxy rings with 10- undecylenic acid increases as [COOH]/[EPOXY] decreases. Epoxidized linseed oil (EOC=9.5 %O) is more suitable source of epoxy groups than ESBO (EOC=6.8 %O) because it provides higher functionality of final monomer. Oils with terminal DBs prepared with 10-undecylenic acid had Mn= 2700, f= 3.5 - 5.8, IV= 35- 55% and viscosity 3 – 28 Pa s. These oils were used for crosslinking by hydrosilylation. Azide-alkyne cycloadition continued using octadecene model compounds. It was utilized to produce crosllinked casting resins with triazine rings. This is a promising technology for preparing materials with increased thermal stability and potential semi-conductivity. A paper on the curing of azidated oils with short alkynes was published. 4. Further development of products by metathesis as the most complex technology. Results: Preparation of 9-octadecene (OD) was carried out by self-metathesis of 1-decene in presence of 1st generation Grubbs catalyst in dichloromethane (yield 70.7%, purity 99%). Characterization of 9-octadecene was carried out by FTIR, GC-MS, 1H NMR, 13C NMR and iodine value (IV). It was a mixture of 29% cis- and 71% trans isomers as observed by GC/MS. The compound was used as a model to study cationic polymerization, epoxidation and the reaction with amines. Epoxydized 9-OD was azidated and alkynated with propargyl alcohol to study kinetics and mechanism of cycloadition.

Publications

  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Zoran S Petrovic, Xianmei Wan, Olivera Bilic, Alisa Zlatanic, Jian Hong, Ivan Javni, Mihail Ionescu, Jelena Milic & Darin Degruson, Polyols and polyurethanes from crude algal oil, J Am Oil Chem Soc 90:10731078.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2013 Citation: Jian Hong, Zoran S. Petrovic, DooPyo Hong, Ivan Javni, Jin Song, The effect of reaction conditions on the hydroformylation of soybean oil, 2013 Pentasectional Meeting of the American Chemical Society, March 8-9, 2013,Tulsa, OK.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2013 Citation: Jelena Milic and Zoran S. Petrovic, Polymerized Vegetable Oils as Plasticizers for Rubber, 2013 Pentasectional Meeting of the American Chemical Society, March 8-9, 2013,Tulsa, OK.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2013 Citation: Xianmei Wan, Mihail Ionescu and Zoran S. Petrovic, Determination of iodine value of polymerized vegetable oils by fourier transform-near infrared, 2013 Pentasectional Meeting of the American Chemical Society, March 8-9, 2013,Tulsa, OK.
  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Mihail Ionescu and Zoran S.Petrovic, From Cashew Nut Shell Liquid (CNSL) to Polyols for Polyurethanes, INFORM (2013) June 24 (6), 393-398.
  • Type: Journal Articles Status: Published Year Published: 2013 Citation: D. Radojcic, M. Ionescu, Z. S. Petrovic, Novel Potentially Biodegradable Polyurethanes From Bio-Based Polyols, Contemporary Materials, IV-1, p9-21.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2013 Citation: Zoran S Petrovic, Jian Hong, Alisa Zlatanic, Jelena Milic, Ivan Javni and Olivera Bilic, Polyurethanes from algal oil, 2013 Pentasectional Meeting of the American Chemical Society, March 8-9, 2013,Tulsa, OK.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2013 Citation: Alisa Zlatanic, Biobased polymers via hydrosilylation, 2013 Pentasectional Meeting of the American Chemical Society, March 8-9, 2013,Tulsa, OK.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2013 Citation: Mihail Ionescu, Zoran S. Petrovic, Cationic copolymerization of biological oils, 245th ACS National Meeting & Exposition - April 7-11, 2013, New Orleans, LA.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2013 Citation: M. Ionescu, D. Hong, X. Wan, I. Javni, N. Bilic, Z. Petrovic , New Polyols for Polyurethanes Based on Cashew Nut Shell Liquid, 104th AOCS Annual Meeting & Expo, Montreal April 28-May 1, 2013.


Progress 09/01/11 to 08/31/12

Outputs
OUTPUTS: Our goal for this project is to develop efficient and economic technologies to convert renewable, bio-based oils and fatty acids to new products. Specifically, to develop products based on direct reactions with the double bonds found in bio-based oils. The plan for the second year of research included the following activities: a) cationic polymerization of oils to obtain polymeric oils for applications as extenders in rubber, modifiers for asphalt, printing inks and as solid (gels) or to make polyacids or polyamines as flexibilizing curing agents for epoxy resins; b) hydrosilylation curing of oils and oils with terminal double bonds as potential coating materials; c) metathesis of oil to make new monomers (diacids, oils with terminal double bonds and model compounds with internal double bonds for studying reactions of double bonds); d) addition of phenol to oil and fatty acids to introduce aromatic rings which can react with a number of compounds to give new polyols or new phenolic resins; and e) investigate feasibility of utilizing algal oils for polymeric applications. This year's program involved testing new catalysts (triflic acid, aluminium phenolates, Nafion resins etc.); use of more reactive phenols; testing the relative reactivity of different types of double bonds and utilization of high excess of phenol. The results and progress were presented at the ACS & AOCS Annual Meetings, United Soybean Board TAP meeting, BioEnvironmental Polymer Society Conference, and other International conferences. Other constituents that received information: KS Dept of Commerce, KS Bioscience Authority, the Governor's office, PSU visiting dignitaries, local high school students, and PSU Plastic Engineering students. PARTICIPANTS: Zoran Petrovic, Ph.D., Principal Investigator, planned and directed the research, evaluated results, disseminated the results at various meetings and participated in writing; Ivan Javni, Ph.D., Senior scientist, conducted research using hydroformylation of corn oil, characterization of algae oils, selected experiments and evaluated results; Mihail Ionescu, Ph.D., Senior scientist, conducted research in cationic polymerization of oils and fatty acids, selected the experiments and evaluated the results; Alisa Zlatanic, MSc., Senior Scientist, research on hydrosilylation, tested properties and evaluated the results; Qiang Luo, Ph.D., Research Associate, conducting research on preparation and curing of vinyl compounds from vegetable oils; Jian Hong, Ph.D., Research Associate, metathesis tests and click chemistry experiments; Jelena Milic, MSc., Research Associate, research on algal oil, ozonolysis and polymerization of oils and fatty acids and their inclusion into rubber; Xianmei Wan, MSc., Research Associate, carried out analytical wet chemistry tests for all groups; Darin DeGruson, MSc., Research Associate, Epoxidation of Alpha Olefins, Polymers from algae oil; Manmohan Deep Sandhu, MSc., Research Assistant, research on new isosorbide derivatives for biobased polyurethanes; Nikola Bilic, Graduate Student, assisted Senior Scientist; Olivera Bilic. Graduate Student, assisted Senior Scientist; Dragana Radojcic, Graduate Student, assisted Senior Scientist. TARGET AUDIENCES: Through the course of this project, we shared the general scope and descriptions of this effort with high school groups, college undergraduate and graduate students, and faculty from PSU's Plastics Technology and chemistry departments. Presentations were made throughout our region to local civic groups, the Kansas Department of Commerce and the Kansas Bioscience Authority. 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, and many industrial contacts. PROJECT MODIFICATIONS: Nothing significant to report during this reporting period.

Impacts
The testing of new catalysts showed that alkylation of phenols was improved with fatty acids containing one double bond. The reaction rate was in the order m- cresol>phenol>guaiacol. The product of Friedel Crafts alkylation of phenols with double bonds of vegetable oils is a mixture of alkylated oligomers, fatty acid phenyl esters and unreacted vegetable oil. The structures with two and three non-conjugated double bonds lead preferentially to oligomers and not to alkylated products. Ester bonds are not inert in the presence of phenols leading to a partial formation of phenyl esters (<10%). Triflic acid catalyst is superior to HBF 4 for phenol alkylation with alkenes, but the latter gives a reasonable yield in alkylated products. In addition, a series of polymer networks were prepared reacting silicon-hydride functionalized compounds with different allyl-derivatives of triglycerides and isosorbide. Unsaturated co-monomers were: 1) allyl derivatives of soybean and linseed oils, 2) corn oil-based monomer obtained in the reaction of polyol and allyl glycidyl ether and 3) isosorbide diallyl ether. Five commercial silicon-hydride compounds were used as crosslinkers. Hydrosilylation reactions were carried out in bulk and in toluene. A molar ratio of silicon hydride to double bonds varied between 1 and 1.2. Efficiency of crosslinking increased when resins were cast from solution. Resins derived from isosorbide diallyl ether have lower onset of thermal degradation but much higher residue than triglyceride-based networks. The best moisture resistance was observed in triglyceride-based networks crosslinked with Q resin, while networks containing isosorbide residues were more hydrophilic. Co-metathesis of soybean oil with ethylene was investigated with the aim of making oils with terminal double bonds. Metathesis was carried out with tungsten catalyst, as well as, Grubb's II catalyst. Tungsten catalysts were shown to produce good results at a lower price. Oils with terminal double bonds were copolymerized with maleic anhydride or crosslinked by hydrosilylation. The crude algal oil (AO) used in this work had low unsaturation, high content of free fatty acids and small amount of polyunsaturated fatty acids. Epoxidation, hydroformylation, ozonolysis and transesterification of AO was successful. Polyols were obtained from methanol ring-opened epoxidized AO which were used to make relatively good elastomers and rigid foams. Polyols by hydroformylation of AO were very reactive and could be used for spray applications. Ozonolysis gave some useful monomers. The results were reported at an international symposium. Several students have been involved in the project.

Publications

  • Ionescu, M., Wan, X., Bilic N., and Petrovic, Z.S., 2012. Polyols and rigid polyurethane foams from cashew nut shell liquid, J Polym. Environment, published online: DOI 10.1007/s10924-012-0467-9.
  • Hong, J., Shah, B.K., and Petrovic, Z.S., 26 July 2012. Vegetable Oil Cast Resins via Click Chemistry: Effects of Cross- Linkers, Europ. J. Lipid Chem. Technol. First published online: DOI: 10.1002/ejlt.201200143.
  • Hong, J., DeGruson, D., Petrovic, Z.S., 2011. Poster presentation, Effect of Different Oxidants on Epoxidation of Alpha Olefins, 46th Midwest 39th Great Lake Joint Regional ACS Meeting, St. Louis, MO.
  • Petrovic, Z.S., Hong, J., Shah, B.K., 2012. Conference presentation, Polymers from vegetable oils by click chemistry, 5th Workshop on Fats and Oils as Renewable Feedstock for the Chemical Industry, Krlasruhe, Germany.
  • Petrovic, Z.S., Hong, J., Shah, B.K., 2012. Conference presentation, Novel Vegetable Oil-Based Cast Resins, United Soybean Board TAP meeting, Detroit, MI.
  • Petrovic, Z.S., Wan, X., Zlatanic, A., Hong, J., Javni, I., Ionescu, M., Milic, J., DeGruson, D., and Hong, D., 2012. Conference Poster, Polymers from algae oil, 103rd AOCS Annual Meeting and Expo, Long Beach, CA.
  • Petrovic, Z.S., Hong, J., Javni, I., and Bilic, O., 2012. Conference presentation, Polymeric materials from algae oil, Fourteenth Annual Yucomat 2012 Conference, Herceg Novi, Montenegro.
  • Zlatanic, A., Ionescu, M., Wan, X., Petrovic, Z.S., 2012. Poster presentation, Biobased polymer networks via hydrosilylation, 20th Anniversary Celebration of the BioEnvironmental Polymer Society, Denton, TX.
  • Hong, J., Luo, Q., Wan, X., Petrovic, Z.S., and Shah, B.K., 2012. Biopolymers from Vegetable Oils via Catalyst- and Solvent-Free Click Chemistry: Effects of Cross-Linking Density, Biomacromolecules , 13 (1), pp 261-266.
  • Petrovic, Z.S., Cvetkovic, I., 2012. Vegetable oil-based hyperbranched polyols in flexible foams, Contemporary Materials, III-1, 63- 71.
  • Petrovic, Z.S., Cvetkovic, I., Milic, J., Hong, D., and Javni, I., 2012. Hyperbranched polyols from hydroformylated methyl soyate, JAppl.Polym.Sci., 125(4), 2920-2928.
  • Milic J., Teraoka, I., and Petrovic, Z.S., 2012. Solution properties of bio-based hyperbranched polyols investigated by multiple detection size exclusion chromatography, JAppl.Polym.Sci., 125, Issue S2, pages E586-E594.
  • Luo, Q., Liu, M., Xu, Y., Ionescu, M., and Petrovic, Z.S., 5 Jan 2013. Thermosetting allyl resins derived from soybean fatty acids, Journal of Applied Polymer Science (Journal of Applied Polymer Science, 127(1), pages 432-438, Article first published online: 27 APR 2012 DOI: 10.1002/app.37814.
  • Luo, Q., Liu, M., Xu, Y., Ionescu, M., and Petrovic, Z.S., 2011. Thermosetting Allyl Resins Derived from Soybean Oil, Macromolecules, 44, 7149-7157.
  • Ionescu, M., and Petrovic, Z.S., 2011. Phenolation of vegetable oils, J. Serb. Chem. Soc. 76 (4) 591-606.
  • Petrovic, Z.S., and Yemul, O., 2011. Conference presentation, Thermoplastic Elastomers from Modified Oleic Acid, World Conference on Oilseed Processing, Fats & Oil Processing, Biofuels &Applications, Izmir, Turkey.
  • Petrovic, Z.S., Cvetkovic, I., 2011. Conference Presentation, Polyurethane networks from renewable hyperbranched polyols, International Scientific Conference Contemporary Materials 2011, Banja Luka, Bosnia and Hercegovina.


Progress 09/01/10 to 08/31/11

Outputs
OUTPUTS: This project will develop efficient and economic technologies to convert renewable, bio-based oils and fatty acids to new products. Specifically, we will develop direct reactions with the double bonds found in bio-based oils. The resulting materials will be used as polymeric materials and building blocks for large markets with specialty and commodity applications. Bio-based starting materials will include oils and acids derived from soybeans, algae, and other naturally occurring, renewable feedstocks. Product areas will include monomers, oligomers and polymers that could be used as specialty oils, lubricants, additives and coatings. Vegetable and other bio-based oils contain internal double bonds which are less reactive and not readily polymerizable. This project focused on transformations that convert these oils into products in a single step, including cationic polymerization, hydrosilylation, metathesis, and the addition of phenol. This project will lead to materials made from 100% vegetable oils or to co-polymerized products with specific properties. The benefits from this project include: (1) a reduction in U.S. dependence upon foreign petroleum by replacing petroleum-based feedstocks for plastics with bio-based feedstocks, (2) the creation of new uses for renewable, U.S. agricultural commodities such as soybeans and algae, and (3) development of new, green materials that will compete in the marketplace. Feedstocks based on plant-based oils have the advantage of more stable agricultural prices, and consumption of these oleochemicals is estimated to be several hundred thousand tons per year. Four different sub-projects were started: 1. Cationic polymerization of oils and phenolation of oils; 2. Hydosilylation; 3. Co-metathesis with ethylene and 4. Algal oil products. The results and progress on this project have been shared with a variety of constituents in the state of Kansas, through national and international technical meetings, through written publications, and with partner industries. 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). 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. Specifically, we have worked with a variety of algae companies (including Solix Biosystems, Inc. in Ft. Collins, CO) to secure samples of algal oil for analysis and investigations. The Lord Corporation has investigated our polymerized oils as additives for rubber formulations. PARTICIPANTS: Zoran Petrovic, P.I. Directed research, review results, planning experiments. Ivan Javni, Senior Associate, Characterization of algal oils useful for industrial applications. Mihail Ionescu, Senior Associate, Polymerization and phenolation of vegetable oils. Alisa Zlatanic, Senior Associate, Hydrosililation. Changhong Zhang, Post Doc, Metathesis of oils, epoxidation of terminal epoxides. Darin DeGruson, Research Associate, Chromatographic characterization of methylated hydroformylated soybean oil, and Co-metathesis of fatty acids. Xianmei Wan, Research Associate, Characterization of sulfur-containing polyols for flexible polyurethane foams. Olivera Bilic, Graduate Assistant, Practicum Training, Assisted Senior Associate in the characterization of Algal Oils. Dragana Radojcic, Graduate Assistant, Assisted Senior Associate in the characterization of monomers and polymers. 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: Nothing significant to report during this reporting period.

Impacts
Cationic polymerization of oils in presence of fluoroboric acid at low temperatures and room pressure was achieved. Polymerized oils of varying molecular weights and viscosities were obtained. The mechanisms of polymerization were elucidated and samples of oils were incorporated as plasticizers in rubber. It has been shown that polymerized oils are viable substitutes for mineral oils but they are more economical and can copolymerize with rubber. This direct bonding with elastomer chains makes our additives permanent (i.e., no leaching). A chapter in a book was published and conference papers were presented. Phenolation of vegetable oils is another process which allows introduction of aromatics into the vegetable oil structure. While polymerization of oils proceeds easier in oils containing fatty acids with two or three double bonds, phenolation proceeds easier in oils with only one double bond (oleic acid). Phenolic groups in the structure then allows different reactions such as the preparation of polyols (by propoxylation, ethoxylation, or Mannich reactions). Polyols were prepared and used for flexible polyurethane foams. A paper on phenolation was published. The co-metathesis of soybean oil with ethylene was investigated with the goal to make oils with terminal double bonds. Metathesis was carried out with tungsten catalysts, and Grubb's catalyst was also tried. Tungsten catalysts were shown to produce good results at a lower price. These oils with terminal double bonds are being used to copolymerize with maleic anhydride or for hydrosilylation reactions. The hydrosilylation of oils with internal double bonds has been carried out with a range of silylating agents. It was concluded that internal double bonds are inactive in this reaction. Thus, oils with terminal double bonds were prepared by metathesis or by reacting epoxidized oils with allyl alcohol. 1-decene was used as model compound to study the degree and kinetics of hydrosilylation. This work is still in progress. The chemistry of algal oil was thoroughly investigated. The composition of a commercial algal oil was analyzed and found that it contains large amount of free fatty acids as well as high content of saturates. Epoxidation of algal oils did not proceed to the same extent as epoxidation of vegetable oils. The epoxidized oil was however, successfully converted to polyols and polyurethanes. Ozonolysis of algal oil was successfully carried out but the product - the polyol had a lower OH number. Hydroformylation of algal oil was successful and the polyols is being tested in polyurethanes. Cationic polymerization of algal oil under the same conditions as in vegetable oils did not proceed as expected and the conditions will be changed. To our knowledge this is the first time that these chemistries are applied to algal oils. The results will be reported at the next American Oil Chemist Symposium.

Publications

  • Ionescu Mihail and Petrovic S. Zoran, 2011. Polymerization of Soybean Oil with Superacids, Soybean - Applications and Technology, Tzi-Bun Ng (Ed.), ISBN: 978-953-307-207-4, InTech, Available from: http://www.intechopen.com/articles/show/title/polymerization-of-soybe an-oil-with-superacids.
  • Mihail Ionescu and Zoran S. Petrovic 2011, Phenolation of vegetable oils, J. Serb. Chem. Soc. 76 (4) 591-606.
  • Z.S.Petrovic, 2010. Polymers from biological oils, Contemporary Materials, I-1, 39-50.
  • Kamal Aly, D. Degruson, Z. Petrovic, October 2010. Co-metathesis of methyl oleate and ethylene using homogeneous catalysts, ACS-45th Midwest Regional Meeting, Wichita, KS.
  • D. Degruson, I. Cvetkovic, Z.S. Petrovic, October 2010. Chromatographic characterization of methylated hydroformylated soybean oil, ACS-45th Midwest Regional Meeting, Wichita, KS.
  • M. Ionescu, X. Wan, Z. S. Petrovic, March 2011. Sulfur-Containing Polyols for Flexible Polyurethane Foams, 56th Annual Pentasectional ACS Meeting, Bartlesville, OK.
  • Z. Petrovic, James R. Halladay, April 2011. Soybean oil plasticizers as replacement of petroleum oil in rubber, United Soybean Association (USB), Technical Advisory Panel, Detroit, Mich.
  • Javni, O. Bilic, Z.S. Petrovic, May 2011. Characteristics of Some Algal Oils Useful for Industrial Applications, 102nd AOCS Annual Meeting & Expo, Cincinnati, OH.