Source: UNIVERSITY OF GEORGIA submitted to NRP
NEW POLYMERS FROM CAMELINA OILS FOR APPLICATIONS IN PACKAGING COATINGS AND FLOOR COVERING PRODUCTS
Sponsoring Institution
National Institute of Food and Agriculture
Project Status
COMPLETE
Funding Source
Reporting Frequency
Annual
Accession No.
1010262
Grant No.
(N/A)
Cumulative Award Amt.
(N/A)
Proposal No.
(N/A)
Multistate No.
(N/A)
Project Start Date
Aug 1, 2016
Project End Date
Jul 31, 2020
Grant Year
(N/A)
Program Code
[(N/A)]- (N/A)
Recipient Organization
UNIVERSITY OF GEORGIA
200 D.W. BROOKS DR
ATHENS,GA 30602-5016
Performing Department
College of Family & Consumer Sciences
Non Technical Summary
In the United States, widespread attention given to recyclability and environmentally friendly materials underscores growing interest in the development of sustainable, agricultural products with properties comparable to traditional petroleum-based coating/composites/plastics. Plant oils, as abundant, renewable resources, have the potential to replace petroleum as a chemical feedstock. Epoxidized camelina oil could make a good polymer coating with similar functional performance to petroleum resin when used for packaging, hard surface flooring, and binders in carpet matrices. The rationale underlying this project is that its successful completion will catalyze a vertical step in agricultural-based, value-added products. Our objectives include 1) developing expodized camelina oil coating formulations, evaluating their performance properties, cost effectiveness, and VOC generation, and comparing their properties to epoxidized soybean oil and petroleum-derived polyesters (polyolefins); and 2) investigate the specific, potential use of the epoxidized camelina oil resin in packaging, hard floor covering, and carpet binder applications. The proposed research will contribute in-depth understanding of the properties, performance, and cost competitiveness of epoxidized camelina oil formulations especially in flooring or packaging applications. The epoxidized camelina oil resins are expected to present commercial and environmental advantages, such as low cost, recyclability, carbon dioxide-neutrality, and biodegradability. Farmers, manufacturers, and consumers have potential to benefit from the creation of a market for sustainable, renewable resins made from camelina oil.
Animal Health Component
25%
Research Effort Categories
Basic
50%
Applied
25%
Developmental
25%
Classification

Knowledge Area (KA)Subject of Investigation (SOI)Field of Science (FOS)Percent
51118992000100%
Goals / Objectives
This hatch research project addresses the National Institutes of Food and Agriculture's Critical Agricultural Materials initiative, which seeks "to develop and demonstrate industrial polymers that are manufactured from domestically produced agricultural materials and are of strategic and industrial importance to benefit the economy, defense, and general well-being of the nation" as well as the objectives #3.1(a) of the multistate project 1054, "Biobased Fibrous Materials and Cleaner Technologies for a Sustainable and Environmentally Responsible Textile Industry." Polymer resins and their innovative applications have increasing significance in the industrial and commercial fields. Polymer resins are generally synthesized from petroleum-based feedstock chemicals. However, plant oils, which are abundant, renewable resources, have the potential to replace or substitute for petroleum as a chemical feedstock (Can et al., 2006; Zhao et al., 2008). Although petroleum-based coating resins are durable and have barrier resistance properties, they can cause leaching and have organic volatiles (VOCs) with toxicity and/or environmental implications. Therefore, a need exists for fundamental research to develop coating formulations from sustainable resources which can provide consistent performance and have similar properties to petroleum-based coating materials.Epoxidized camelina oil could make a good polymer coating with similar functional performance to petroleum resin when used for packaging, hard surface flooring, and binders in carpet matrices. Camelina sativa is a fast-growing, low input plant that can be grown in poorer soils with minimal water, fertilizer, or pesticide requirements. Its tolerance for cold gives it potential for use as season rotational crop in Southeastern US and other temperate climates. Camelina oil is primarily used in the biodiesel industry. Camelina oil is a good alternative to other vegetable oils, such as soybean oil, because it will not compete with the food oil market. Finally, camelina oil is highly unsaturated which makes it an ideal candidate for epoxidation and chemical transformation into effective coatings and a competitive choice to soybean oil with its similar level of unsaturation (Abramovic and Abram, 2005; Gunstone (Ed.), 2011). The rationale underlying this project is that its successful completion will catalyze a vertical step in agricultural-based, value-added products. Goals / Objectives:Objective #1: Develop expodized camelina oil coating formulations, evaluate their performance properties, cost effectiveness, and VOC generation, and compare their properties to epoxidized soybean oil and petroleum-derived polyesters (polyolefins).Objective #2: Investigate the specific, potential use of the epoxidized camelina oil resin in packaging, hard floor covering, and carpet binder applications.
Project Methods
To achieve objectives #1 and #2, we plan to perform the following studies:Study 1: Camelina oils purchased through commercial sources will be analyzed for fatty-acid profile, water content and free fatty-acid content. High unsaturation in camelina oils due to the presence of fatty acids, such as linoleic and linolenic, make them appropriate for epoxidation. Unsaturated fatty acids have at least one double bond that can be easily epoxidized using hydrogen peroxide through hydrogen peroxide-catalyzed, acid-catalyzed, or chemoenzymatic processes. The first two methods are being used in industry, but have the following disadvantages: side reactions via oxirane opening leading to lower selectivity and corrosion problems due to the strong acid. However, this process can be made cleaner by using heterogeneous catalysts (e.g., ionic resins) or biocatalysts such as enzymes (e.g., lipase B of Candida antartica immobilized on a macroporous support). We will use both heterogeneous catalysts and enzymes to develop a method that is a solvent free and environmentally friendly method for production of epoxidized camelina oils. For instance, a known quantity of oil, acetic acid and heterogeneous catalyst will be mixed for 5 min, followed by dropwise addition of aqueous solution of H2O2. The reaction will be carried out for 5 h at 500 rpm. Then, the catalyst will be filtered out, followed by alkaline and water rinsing to remove free fatty acid and excess H2O2. The final organic phase will be dried and characterized for oxirane number, iodine value and selectivity. Processing variables, such as acetic acid:unsaturation ratio, H2O2:unsaturation ratio, concentration of H2O2, concentration of catalyst and temperature, will be optimized using a factorial design method. The response variable will be the degree of epoxidation (or oxirane number). The method stated above will be compared with the traditional industrial method using in situ peroxy acids catalyzed by a catalyst such as sulfuric acid. Oil, acetic acid and sulfuric acid will be added in a three neck flask with stirring for 30 min and aqueous H2O2 will be added dropwise over 30 min with continuous stirring. The resulting samples will be extracted using diethyl ether followed by rinsing with water.Study 2: Another important component of resin oil formulation is the curing/hardening agent. The synthesis of a novel curing agent, N-benzyl pyrazinium hexafluoroantimonate (BPH), to cure epoxidized oil resins will be adopted from a literature method by Park et al. (2004). The required amount of BPH curing agent will be dissolved in acetone, and then epoxidized oils will be added, stirred, and degassed for the molding process. Thermal experiments will be conducted in the differential scanning calorimetery and thermogravimetric analyzer and dynamic mechanical thermal analyzer to determine the curing/conversion extent of the resin and thermal transitions into the biothermoset matrix. This testing will help in optimizing the amount of curing hardener (0.5-5% of resin weight) used in the resin. In addition, thermal analyses will enable us to observe chemical changes such as oxidation and degradation. Further, dynamic mechanical analysis (DMA) of small, thermomechanically molded specimens will be tested for the mechanical performance over a temperature range spanning from subambient to 400 °F. Unmodified camelina oils along with curing agents will be used as controls. Factorial design method of statistics will be used to evaluate the impact of the following factors on the mechanical performance: level of oil epoxidation, amount of shear thinning agent and curing agent, and temperature of curing experienced during the extrusion coating process. In addition, the results will be interpreted using table of contrast coefficients to determine the most important factor. Resin Transfer Molding (RTM) injection and/or compression molding systems will be used for making lab-scale, coating plastic samples. Key physical and thermal properties of the developed coating material will be tested. Performance criteria of plastics, such as tensile strength and modulus (both quasi-static and dynamic) will be evaluated using standard test methods (e.g., ASTM or industry wide methods) that are prevalent in the packaging industries. Volatiles analysis will be conducted and compared to reported limit by static headspace using GC-MS instrumentation. The toxicity of the epoxidized camelina oil/BPH formulations will be tested for potential food packaging applications. Control samples of plastics from petroleum derived polyesters or polyolfeins will be produced for benchmarking. We will also compare epoxidized camelina oil with epoxidized soybean oil. At the conclusion of these studies, we expect to confirm the potential of camelina oil as a feedstock for polymer coatings and adhesives along with the appropriate formulation of these epoxidized oils to meet the desired performance characteristics of bioresins in packaging and other coating applications.Study #3: The presence of volatile organic compounds (VOCs) generated during thermal processing and use is an area of concern for food and non-food contact packaging and the carpet and flooring industries. The identification of volatile compounds and quantitative comparison of VOC's reduction for treated (both coated and laminated on lab-scale) and untreated samples will be performed via specialized gas chromatography and mass spectrometry (GC-MS) instrumentation. The results will be quantified to establish the efficacy of the camelina oil-based coating resins. This study is aimed at product development for resin formulations to be used in specific film applications, such as agricultural mulch films, food and non-food contact paper-based packaging, hard surface flooring coating and carpet backings. The coating resin formulations will be tested for their durability against environmental conditions and substrates of interest (interfacial stability). The base substrates under evaluation for this study are paperboard for packaging application, algae/LLDPE thermoplastic based mulch films for agricultural application (in collaboration with Algix, LLC), and hard surface flooring coatings and lamination of carpet backings for flooring applications. The coated and laminated substrates will be evaluated for their resistance to delamination at the interfacial region, volatiles, leaching, degradation, stiffening, and effects on tensile strength. The analysis conducted will include dynamic mechanical analysis (DMA), tensile strength, water stability, and scanning electron microscopy (SEM). Molecular level studies will be conducted using AFM to evaluate interfacial properties. The data from the performance analysis will be entered into a database to compare epoxidized camelina oil-based resin formulations on performance properties.ReferencesMeier, M. A. R., Metzger, J. O., and Schbert, U. S., Plant Oil Renewable Resources as Green Alternatives in Polymer Science, Chem. Soc. Rev., 36, 1788-, 2007.Park, S-. J., Jin, F-. L., and Lee, J-. R., Synthesis and Thermal Properties of Epoxidize Vegetable Oil, Macromol. Rapid Commun., 25, 724-, 2004.

Progress 08/01/16 to 07/31/20

Outputs
Target Audience: Nothing Reported 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? Nothing Reported What do you plan to do during the next reporting period to accomplish the goals? Nothing Reported

Impacts
What was accomplished under these goals? We studied various conversion methods of epoxidizing the camelina oils for creating biobased coatings. We used an environmentally-friendly enzymatic process for converting the unsaturation of camelina oil into epoxy groups. We were able to prepare resin formulation for the next step of use in packaging, hard floor covering, and carpet binder applications through the product development.

Publications


    Progress 10/01/18 to 09/30/19

    Outputs
    Target Audience: Nothing Reported 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? Nothing Reported What do you plan to do during the next reporting period to accomplish the goals?Future work will focus on studying the effect of hardening agents (such as maleic anhydride or benzyl pyrazinium hexafluroantimonate) on the mechanical, thermal, and viscoelastic properties of cured epoxidized camelina oil. We will also research on identifying green hardener for curing epoxidized vegetable oil fomulation. Another important component of resin oil formulation is the curing/hardening agent. The synthesis of a novel curing agent, N-benzyl pyrazinium hexafluoroantimonate (BPH), to cure epoxidized oil resins will be adopted from a literature method by Park et al. (2004). The required amount of BPH curing agent will be dissolved in acetone, and then epoxidized oils will be added, stirred, and degassed for the molding process. Thermal experiments will be conducted in the differential scanning calorimetry and thermogravimetric analyzer and dynamic mechanical thermal analyzer to determine the curing/conversion extent of the resin and thermal transitions into the biothermoset matrix. This testing will help in optimizing the amount of curing hardener (0.5-5% of resin weight) used in the resin. In addition, thermal analyses will enable us to observe chemical changes such as oxidation and degradation. Further, dynamic mechanical analysis (DMA) of small, thermomechanically molded specimens will be tested for the mechanical performance over a temperature range spanning from sub ambient to 400 °F. Unmodified camelina oils along with curing agents will be used as controls. The Factorial design method of statistics will be used to evaluate the impact of the following factors on the mechanical performance: level of oil epoxidation, amount of shear- thinning agent and curing agent, and temperature of curing experienced during the extrusion coating process. In addition, the results will be interpreted using the table of contrast coefficients to determine the most important factor. RTM (Resin Transfer Molding) injection and/or compression molding systems will be used for making lab-scale, coating plastic samples. The Key physical and thermal properties of the developed coating material will be tested. Performance criteria of plastics, such as tensile strength and modulus (both quasi-static and dynamic), will be evaluated using standard test methods (e.g., ASTM or industry-wide methods) that are prevalent in the packaging industries. Volatiles analysis will be conducted and compared to the reported limit by static headspace using GC-MS instrumentation. The toxicity of the epoxidized camelina oil/BPH formulations will be tested for potential food packaging applications. Control samples of plastics from petroleum-derived polyesters or polyolefins will be produced for benchmarking. We will also compare epoxidized camelina oil with epoxidized soybean oil. At the conclusion of these studies, we expect to confirm the potential of camelina oil as a feedstock for polymer coatings and adhesives along with the appropriate formulation of these epoxidized oils to meet the desired performance characteristics of bio resins in packaging and other coating applications.

    Impacts
    What was accomplished under these goals? A peroxy acid method with a heterogeneous catalyst or ionic resin was used to convert camelina oil to epoxidized camelina oil. The optimized epoxidation parameters (0.5:1 acetic acid: unsaturation, 50% hydrogen peroxide, and 25% resin) for camelina oil yielded in oxirane content of 7.61%, an iodine value of 1.66 g/ 100 g iodine, and a high conversion rate of 90.9%. Epoxidized camelina oil shows promise as a new raw material for polymer resins. We also worked on the Iodine value and oxirane oxygen content to characterize epoxidized plant oils. Oxirane oxygen content indicates the presence of epoxy groups in the epoxidized oil. Iodine value indicates the degree of unsaturation after the epoxidation reaction.

    Publications

    • Type: Conference Papers and Presentations Status: Published Year Published: 2019 Citation: New Polymer Resins from Camelina Oil, The 4th International Symposium on Materials from Renewables (ISMR), University of Georgia, Athens, GA, October 2019.
    • Type: Conference Papers and Presentations Status: Published Year Published: 2019 Citation: New polymers from camelina oils for applications in packaging coatings, Center for Bioplastics and Biocomposites (CB2), University of Georgia, Athens, GA, May 2019.


    Progress 10/01/17 to 09/30/18

    Outputs
    Target Audience: Nothing Reported 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? Nothing Reported What do you plan to do during the next reporting period to accomplish the goals?Future work will focus on studying the effect of hardening agents (such as maleic anhydride or benzyl pyrazinium hexafluroantimonate) on the mechanical, thermal, and viscoelastic properties of cured epoxidized camelina oil.

    Impacts
    What was accomplished under these goals? Epoxidation of Camelina Oil Epoxidation was carried out in a 500 ml two necked round bottom flask equipped with a mechanical stirrer using a Teflon blade 8 cm in diameter. The flask was heated in an oil. Based on the design of experiments (Table 1), Camelina oil (50 g; 0.571 mol of unsaturation), acetic acid, and Amberlite 120H resin were added to the flask and mixed for 5 minutes at 60?C. Hydrogen peroxide (a 1.65 : 1 molar ratio of hydrogen peroxide to unsaturation) was added drop-wise at 120 mL/hour using a KD scientific syringe pump. The solution was stirred for 5 hours at 500 rpm and 60?C. The resin was filtered out and the aqueous part of the solution separated out and discarded. The samples were then washed with saturated sodium carbonate solution and water at 50?C. The samples were dried with Magnesium sulfate overnight and filtered twice to ensure complete dryness. Table 1: Design of Experiments Factors Reagents A B C AA (ml) H2O2 (ml) Resin (g) Trial AA : U [H2O2] [Resin] 1 0.55: 1.0 30% 10% 9.5 26.9 5.0 2 0.55: 1.0 30% 25% 9.5 26.9 12.5 3 0.55: 1.0 50% 10% 9.5 26.9 5.0 4 0.55: 1.0 50% 25% 9.5 26.9 12.5 5 1.1: 1.0 30% 10% 18.9 48.3 5.0 6 1.1: 1.0 30% 25% 18.9 48.3 12.5 7 1.1: 1.0 50% 10% 18.9 48.3 5.0 8 1.1: 1.0 50% 25% 18.9 48.3 12.5 Iodine Value and Oxirane Oxygen Content The epoxidized camelina oil samples were characterized using oxirane oxygen content (AOCS Official Method Cd 9-57) and iodine value (ASTM Standard Method D5554-15). Percent conversion of double bonds to oxirane group and selectivity for oxirane oxygen were calculated using equations. Characterization of Epoxidized Camelia Oil: Iodine value and oxirane oxygen content are important test parameters used to characterize epoxidized plant oils. Oxirane oxygen content indicates the presence of epoxy groups in the epoxidized oil. Iodine value indicates the degree of unsaturation after the epoxidation reaction. The predicted oxirane oxygen value for Camelina oil is 8.36. Ideally, the experimental oxirane oxygen value will be close to the predicted (percent conversion will approach 100%) and the iodine value will approach zero. Table 2: Properties of Camelina Oil After Epoxidation Trial Oxraine Oxygen Content (%) Iodine Value (g I2/100g) Percent Conversion Selectivity 1 5.37 ± 0.08 30.46 ± 1.04 64.1 0.81 2 7.28 ± 0.31 13.65 ± 2.75 86.9 0.96 3 7.63 ± 0.04 1.74 ± 0.64 91.2 0.92 4 7.61 ± 0.05 1.66 ± 0.13 90.9 0.92 5 7.44 ± 0.37 6.81 ± 2.34 88.9 0.93 6 7.42 ± 0.03 4.00 ± 0.54 88.6 0.91 7 7.47 ± 0.08 0.98 ± 0.59 89.2 0.9 8 6.98 ± 0.01 0.91 ± 0.14 83.3 0.84 The iodine value of Camelina oil is reduced (from 144.84 g I2/100 g) by 79% or higher. The oxirane oxygen content we are reporting range from 6.98 to 7.61%, which correspond to a percent conversion of 64.1 to 91.2%. Kim, Li, and Sun reported a 76.34% conversion rate in the epoxidation of camelina oil using 0.66 molar ratio of formic acid and 1.7 molar ratio of hydrogen peroxide at 50oC for 5 hours. Their epoxy content reached 7.52%. We are reporting a similar epoxy content of 7.63 ± 0.04 at the highest. However, our maximum conversation rate of 91.2% is higher than theirs, most likely due to the presence of Amberlite resin that minimizes the side reactions that can open the epoxy rings. The concentration of hydrogen peroxide appears make the most significant impact in the oxraine oxygen and iodine value. When comparing trials 2 and 4 (with 0.5:1 acetic acid to unsaturation and 25% resin), 50% hydrogen peroxide gives a higher oxirane oxygen and a lower iodine value than 30% hydrogen peroxide (Table 1). If hydrogen peroxide is more dilute, the increase in water can increase the possibility of side reactions occurring. Degradation of epoxy groups gives lower oxirane oxygen values. Likewise, trials 6 and 8 (with 1:1 acetic acid to unsaturation and 25% resin), 50% hydrogen peroxide has a lower iodine value than 30% hydrogen peroxide. For 50% hydrogen peroxide concentration and 25% in Trials 4 and 8, increasing the ratio of acetic acid: unsaturation from 0.5:1 to 1:1 appears to decrease oxygen oxygen content. Results prove similar for trials 3 and 7. Acetic acid can participate in the degradation of epoxy groups, which is what is happening here. Furthermore, acetic acid appears to have more significant impact on iodine value than on oxirane oxygen content. The concentration of resin appears to improve the oxirane oxygen content and iodine value between trials 1 and 2 (with 0.5: 1.0 acetic acid to unsaturation and 30% hydrogen peroxide). However, the concentration of resin does not appear to make a difference between trials 3 and 4, trials 5 and 6. For trials 7 and 8, the increase in resin does not appear deter degradation of epoxy groups as would be expected. The concentration of resin does not appear to be significant. The optimized conditions for the epoxidation of Camelina oil appear to be 0.5:1 acetic acid: unsaturation, 50% hydrogen peroxide, and 25% resin. In conclusion of this study, a peroxy acid method with a heterogeneous catalyst or ionic resin was used to convert camelina oil to epoxidized camelina oil. The optimized epoxidization parameters (0.5:1 acetic acid: unsaturation, 50% hydrogen peroxide, and 25% resin) for camelina oil yielded in oxirane content of 7.61%, an iodine value of 1.66 g/ 100 g iodine, and a high conversion rate of 90.9%. In conclusion, epoxidized camelina oil shows promise as a new raw material for polymer resins.

    Publications


      Progress 10/01/16 to 09/30/17

      Outputs
      Target Audience:The target audience includes industry such packaging, carpet and rug, coating and resin. 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?Results were disseminated at the Fiber Society 2017 Fall Meeting and Technical Conference in Athens, GA and the NSF IUCRC planning meeting at the University of Georga, February 6-7. What do you plan to do during the next reporting period to accomplish the goals?Using the optimal conditions camelina oil and soybean oil will be epoxidized with the solventless acid ion exchange resin method to in order to compare the properties of soybean oil with camelina oil. Both camelina and soybean oil will be evaluated for oxirane oxygen content, iodine value (before and after epoxidation), percent conversion, and selectivity. Another important component of resin oil formulation is the curing/hardening agent. Using the epoxidized oils, we will investigate the effect of different curing agents (such as benzyl pyrazinium hexafluroantimonate) on the mechanical, thermal, viscoelastic properties of cured epoxidized agents. We will investigate, using factorial design, the factors such as the concentration of curing agent and temperature of curing.

      Impacts
      What was accomplished under these goals? Camelina oil was epoxidized with a solventless acid ion exchange resin method. Processing variables, such as acetic acid: unsaturation ratio (AA:Unsat), concentration of hydrogen peroxide ([H202]), concentration of an ion exchange resin ([Resin]) were studied for the purpose of optimization using a factorial design method. Table 1 Trial AA:Unsat [H2O2] [Resin] Oxraine Oxygen %Conversion Iodine Value % Selectivity 1 0.5: 1.0 30% 10% 5.37 ± 0.08 64.1 30.46 ± 1.04 0.81 2 0.5: 1.0 30% 25% 7.28 ± 0.31 86.9 13.65 ± 2.75 0.96 3 0.5: 1.0 50% 10% 7.63 ± 0.04 91.2 1.74 ± 0.64 0.92 4 0.5: 1.0 50% 25% 7.61 ± 0.05 90.9 1.66 ± 0.13 0.92 5 1.0: 1.0 30% 10% 7.44 ± 0.37 88.9 6.81 ± 2.34 0.93 6 1.0: 1.0 30% 25% 7.42 ± 0.03 88.6 4.00 ± 0.54 0.91 7 1.0: 1.0 50% 10% 7.47 ± 0.08 89.2 0.98 ± 0.59 0.90 8 1.0: 1.0 50% 25% 6.98 ± 0.01 83.3 0.91 ± 0.14 0.84 Iodine value and oxirane oxygen content are important test parameters used to characterize epoxidized plant oils. Oxirane oxygen content indicates the presence of epoxy groups in the epoxidized oil. Iodine value indicates the degree of unsaturation after the epoxidation reaction. The predicted oxirane oxygen value for Camelina oil is 8.36. Ideally, the experimental oxirane oxygen value will be close to the predicted (percent conversion will approach 100%) and the iodine value will approach zero. The iodine value of Camelina oil is reduced (from 144.84 g I2/100 g) by 83.3% or more in Trials 2-8. The oxirane oxygen values we are reporting range (for Trials 2-8) from 6.98 to 7.61, which represent 83.3 to 90.9 percent conversion. The selectivity of the epoxidation reaction (for trials 2-8) is 0.84 or higher. The optimized conditions for the epoxidation of Camelina oil appear to be 0.5:1 acetic acid: unsaturation, 50% hydrogen peroxide, and 25% resin. The concentration of hydrogen peroxide appears make the most significant impact in the oxraine oxygen and iodine value. When comparing trials 2 and 4 (with 0.5:1 acetic acid to unsaturation and 25% resin), 50% hydrogen peroxide gives a higher oxirane oxygen and a lower iodine value than 30% hydrogen peroxide (Table 1). If hydrogen peroxide is more dilute, the increase in water can increase the possibility of side reactions occurring. Degradation of epoxy groups gives lower oxirane oxygen values. Likewise, trials 6 and 8 (with 1:1 acetic acid to unsaturation and 25% resin), 50% hydrogen peroxide has a lower iodine value than 30% hydrogen peroxide. For 50% hydrogen peroxide concentration and 25% in Trials 4 and 8, increasing the ratio of acetic acid: unsaturation from 0.5:1 to 1:1 appears to decrease oxygen oxygen content. Results prove similar for trials 3 and 7. Acetic acid can participate in the degradation of epoxy groups, which is what is happening here. The concentration of resin appears to improve the oxirane oxygen content and iodine value between trials 1 and 2 (with 0.5: 1.0 acetic acid to unsaturation and 30% hydrogen peroxide). However, the concentration of resin does not appear to make a significant difference between trials 3 and 4, trials 5 and 6. For trials 7 and 8, the increase in resin does not appear deter degradation of epoxy groups as would be expected.

      Publications


        Progress 08/01/16 to 09/30/16

        Outputs
        Target Audience:The target audience includes industry such packaging, carpet and rug, coating and resin. 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? Nothing Reported What do you plan to do during the next reporting period to accomplish the goals?With the optimal processing variables, we will scale up our process and repeat the epoxidization using camelina and soybean oil. Both camelina and soybean oil will be evaluated for oxirane oxygen content (before and after epoxidation), iodine value (before and after epoxidation), selectivity, and percent conversion. Another important component of resin oil formulation is the curing/hardening agent. Using the epoxidized oils, we will investigate effect of different curing agents (such as benzyl pyrazinium hexafluroantimonate) on the mechanical, thermal, viscoelastic properties of cured epoxidized agents. We will investigate, using factorial design, the factors such as concentration of curing agent and temperature of curing.

        Impacts
        What was accomplished under these goals? The following experimentation is in progress: Determining the fatty acid profile of camelina oil Epoxidizing camelina oil with acid ion exchange resin method Specifically, a known quantity of camelina oil, acetic acid and heterogeneous catalyst will be mixed for 5 min, followed by dropwise addition of aqueous solution of hydrogen peroxide. The reaction will be carried out for 5 h at 500 rpm at 60oC. Then, the catalyst will be filtered out, followed by alkaline and water rinsing to remove free fatty acid and excess hydrogen peroxide. The final organic phase will be dried and characterized for oxirane number, iodine value and selectivity. Processing variables, such as acetic acid:unsaturation ratio, concentration of hydrogen peroxide, concentration of ion exchange resin will be optimized using the following factorial design method. Run Acetic acid: unsaturation ratio Concentration of hydrogen peroxide Concentration of ion exchange resin 1 1: 0.5 (-) 30% (-) 10% (-) 2 1:1 (+) 30% (-) 10% (-) 3 1: 0.5 (-) 50% (+) 10% (-) 4 1:1 (+) 50% (+) 10% (-) 5 1: 0.5 (-) 30% (-) 25% (+) 6 1:1 (+) 30% (-) 25% (+) 7 1: 0.5 (-) 50% (+) 25% (+) 8 1:1 (+) 50% (+) 25% (+) 9 1: 0.5 (-) 30% (-) 10% (-) 10 1:1 (+) 30% (-) 10% (-) 11 1: 0.5 (-) 50% (+) 10% (-) 12 1:1 (+) 50% (+) 10% (-) 13 1: 0.5 (-) 30% (-) 25% (+) 14 1:1 (+) 30% (-) 25% (+) 15 1: 0.5 (-) 50% (+) 25% (+) 16 1:1 (+) 50% (+) 25% (+) The response variables shall be oxirane oxygen content (before and after epoxidation), iodine value (before and after epoxidation), selectivity, and percent conversion. We are in the process of collecting data so we have no data to report on as of yet.

        Publications