Performing Department
(N/A)
Non Technical Summary
Description of the problem or opportunity: The global market of stretch wrap film is expected to reach $18.46 billion in five years. North America is one of the largest consumers of stretch wrap film. Rising environmental concerns have driven the manufacturers to seek for bio-based substitutes which is compostable or biodegradable from renewable feedstocks.Description of the effort: This project will develop an innovative and sustainable approach to produce low-cost stretch wrap plastic film from CO2 and crude glycerin which are byproducts of the biofuel and bioenergy production. The specific objectives are as follows: (1) Develop an innovative and sustainable approach to produce bio-polycarbonate polymer for stretch wrap film application directly from crude glycerin and CO2; (2) Ter-polymerize bio-epoxide monomer, propylene oxide, and CO2 for improved performance; (3) Characterize and test the biodegradability of stretch wrap film; (4) Analyze the cost for future scale-up application. The proposed technology will not only introduce a cost-effective bioplastic product to the polymer industry, but also improve the economics of the existing biofuel and bioenergy industries.Anticipated Results: At the end of the Phase-I project, a new manufacturing process will be developed to produce bio-based stretch wrap films from CO2 and crude glycerol. It will provide an example of re-thinking and re-designing plastic to the industry. Phase II will build on these results by designing, building and demonstrating a pilot-scale system for the bio-based stretch film production.Commercial Potential: Growing demand for stretch wrap film provides a huge potential market for this technology. More companies are looking to use bioplastics to claim their products as being environment friendly. Large companies such as Nestle and Coca-Cola are looking for biobased plastic to replace the petroleum analogs in their supply chains. Quasar will collaborate with the polymer industry to develop a new bio-based stretch wrap film to meet the growing market needs.
Animal Health Component
0%
Research Effort Categories
Basic
(N/A)
Applied
50%
Developmental
50%
Goals / Objectives
The overall objective of the Phase I research program is to develop an innovative and sustainable approach to produce low-cost stretch wrap plastic film with high yield and excellent properties from CO2 and crude glycerin, which are byproducts of the biofuel and bioenergy production. The specific objectives are as follows:(1) Develop an innovative and sustainable approach to produce bio-polycarbonate polymer for stretch wrap film application directly from fatty acid wastes and CO2(2) Ter-polymerize bio-epoxide monomer, propylene oxide and CO2.(3) Characterize the properties of developed stretch wrap bioplastic film.(4) Test biodegradability of stretch wrap film.(5) Analyze the cost for further scale-up application.
Project Methods
Objective 1: Production of bio-polycarbonate based stretch films from crude glycerin-fatty acid waste and CO2 Task 1.1 Characterize fatty acid wastes Fatty acids wastes from crude glycerin refining may consist of impurities including glycerol, water, FAME (Fatty Acid Methyl Esters), salts and ashes and other unknown impurities. Flue gas CO2 from anaerobic digester may contain impurity gases such as SO2. The fatty acids wastes and CO2 flue gases will be qualitatively and quantitatively characterized with GC, GC-MS and HPLC and trace water meter. The flue gases can pass through a membrane system to obtain clean CO2, and it will be compressed into cylinders for further use.Task 1.2 Produce bio-epoxide monomer The production of bio-epoxide monomer will start with our established procedures with necessary modification. the received fatty acids waste sample (150 g) will be directly dissolved in acetone at the weight ratio of 1:6, and the sodium hydroxide (molar ratio of 1:1.1) will be added dropwise under vigorously stirring at the speed of 500 rpm. With continuously stirring for 4h, a light gray solid will be obtained and filtered from acetone. After drying at 35 °C under vacuum for 48 h to a consistent weight, the light gray particles will be obtained, which is crude glycerin-fatty acids waste derived soap. To produce epoxide monomer, the aforementioned soap of 50 g will be added to a 250 ml three neck flask followed by the addition of epichlorohydrin at a molar ratio (epichlorohydrin to soap) of 8:1, reacted at 115 °C in oil bath until refluxing. Then cetytrimethylammonium bromide will be immediately added and continued reacting for another 2 h. The system will be then cooled down to 70 °C and centrifuged for 10 min at 10,000 rpm. To remove extra epichlorohydrin, the supernatant liquid will be evaporated under vacuum at 60 rpm, 90 °C until no bumping will be observed. The dried bio-based epoxide monomer will be finally obtained by washing with warm water for 3~6 times and distilling at 275 °C ~ 305 °C under vacuum. The used EPCH and acetone will be recycled for reuse.Task 1.3 Production of bio-based stretch filmsThe synthesis of bio-based polycarbonate polymers will be achieved via copolymerization of bio-epoxide monomers (3ml, ~ 3.0g, 0.01mol) obtained in Task 1.2 and CO2 (room temperature, 4MPa) in a clean 10mL autoclave in the presence of Salen(CoCl) catalyst system (catalyst Salen(CoCl) of 0.05 mmol (35 mg) and co-catalyst PPNCl of 0.05mmol (29 mg)) under magnetic stirring at 650 rpm. The autoclave will be filled with dry CO2 at a pressure of 4MPa. After reacting for 24 h under room temperature, the bio-based polycarbonate polymers will be obtained after slowly releasing the residual CO2. To remove catalyst, byproduct and unreacted materials from obtained polymer, dichloromethane solvent of 10 mL will be added to dissolve the obtained bio-based polycarbonates first and transferred to a 500 ml jar, followed by precipitation through dropwise addition of ethanol (90 mL). The purified bio-polycarbonate plastic will be obtained after removing supernatant.Task 1.4 Effects of impurities on the properties of obtained products In this study, different levels of impurities will be added on purpose to investigate the impact of impurities on the yields and performance of bio-based polycarbonate by comparing the results with that from pure fatty acids. Strategies will be developed to mitigate the negative impact of these impurities.Task 1.5 Optimization of operating parametersOptimization of operating parameters will be carried out under copolymerization of bio-monomer from fatty acid waste (FAW) and CO2. A series of reaction will be carried out under different temperatures (22 °C, 45 °C and 60 °C), different reaction times (24 h, 36 h and 48 h) and catalyst loadings (0.02 mmol/3 mL, 0.04 mmol/3 mL, and 0.06 mmol/3 mL). Yield of bio-polycarbonates will be used to optimize the operational parameters. The experimental design is listed in Table 1.Objective 2: Ter-polymerize bio-epoxide monomer, propylene oxide and CO2 The procedure for ter-polymerization of CO2, bio-epoxide monomer and propylene oxide will be similar to the above co-polymerization procedure in Task 1.2. The synthesis of bio-based polycarbonate polymers will be studied with different volume ratio of fatty acid waste monomer to propylene oxide of 2:1, 1:1, and 1:2 (molar ratio of 1:2, 1:4 and 1:8). The total volume for monomers is 3 mL. Poly(propylene carbonate) obtained using only PO as the epoxy monomer under the same condition will be used as control.After polymerization, the obtained products will be dissolved in CH2Cl2 (10 mL) and precipitated with 50 mL ethanol added dropwise. After washing for three times, purified bio-based polycarbonate polymer will be obtained in a milk-white color. Then the bio- polycarbonate films will be produced by applying the purified bio-polycarbonate plastic films on a 15 cm × 15 cm sheet of polytetrafluoroethylene coated aluminum. A square film applicator with a 150 mm gap was used to apply the polymer on PTFE sheet. After drying in open air for one week at room temperature, the films will be cured and peeled off for further test.Objective 3: Characterization Fourier Transform Infrared (FT-IR) tests will be performed on a Spectrum Two IR spectrometer (PerkinElmer Inc., MA) to monitor of the reaction. Gas Chromatography - Mass Spectrometry (GC-MS) spectra will be performed on a Shimadzu GC-MS QP 2010 SE with helium gas as the carrier gas, equipped with a Zebron ZB-FFAP column (30 m × 0.25 mm × 0.2 μm). Molecular weights of polymers will be determined by gel permeation chromatography (GPC) analysis on a Shimadzu LC-20 AB GPC system (Shimadzu, Columbia, MD, U.S.) equipped with an RID-10A refractive index detector, a SPD-M20A prominence photodiode array detector, a Waters Styragel HR1 column (7.8 × 300 mm), and a Phenogel 5 m 10 E4 Å LC column (7.8 × 300 mm). Polystyrene will be employed as the calibration standard. Nuclear magnetic resonance (1H NMR) will be recorded on a Bruker AVIII 400 MHz spectrometer at 400 MHz (Billerica, Massachusetts, U.S.), using Chloroform-D as solvent. Thermal properties will be tested by Differential scanning calorimetry (DSC) and Thermogravimetric analysis (TGA). DSC will be performed on a Q20 DSC analyzer (TA Instruments, New Castle, DE, U.S.) equipped with refrigerated cooling. TGA will be performed on a Q50 thermogravimeter (TA Instruments, New Castle, DE, U.S.) by heating polycarbonate samples from 50 to 650 °C at a rate of 10 °C/min under nitrogen. Mechanical properties, including the tensile strength and elongation rate at break (%), will be determined according to ASTM D 882-12 (ASTM International, 2017) using TA instrument Q800 dynamic mechanical analyzer (TA Instruments, New Castel, DE, U.S.).Objective 4: Test of biodegradability of stretch film Laboratory-scale experiments will be conducted to measure the biodegradability of the obtained stretch wrap bioplastic films through composting in the lab of Quasar Energy Group, LLC. The obtained bio-based stretch films will be cut in 5 x 5 cm2 for composting tests. ?Objective 5: Economic analysis Based on the feedstock and chemical cost, equipment cost, and electricity consumption, a cost analysis will be conducted. The results (capital and operating costs) will be presented based on the optimized condition with performance comparable to petroleum-based products. The key factors that contribute to the product quality and costs will be identified. The mass balances of the proposed technology will be conducted and validated during lab tests. Economic performance will be evaluated based on the following measurable criteria: capacity of the system, feedstock cost (or tipping fees), chemicals, electricity, system up-time, and capital costs.