Source: WASHINGTON STATE UNIVERSITY submitted to NRP
DEVELOPMENT OF NEW POLYMER APPLICATIONS USING BIOREFINERY CO-PRODUCTS AND AGRICULTURAL RESIDUES
Sponsoring Institution
National Institute of Food and Agriculture
Project Status
COMPLETE
Funding Source
HATCH
Reporting Frequency
Annual
Accession No.
0227898
Grant No.
(N/A)
Cumulative Award Amt.
(N/A)
Proposal No.
(N/A)
Multistate No.
(N/A)
Project Start Date
Jan 1, 2012
Project End Date
Dec 31, 2017
Grant Year
(N/A)
Program Code
[(N/A)]- (N/A)
Recipient Organization
WASHINGTON STATE UNIVERSITY
240 FRENCH ADMINISTRATION BLDG
PULLMAN,WA 99164-0001
Performing Department
Composite Materials and Engineering Center
Non Technical Summary
The biorefinery is an emerging technology in which biomass, instead of crude oil, serves as the feedstock for the productions of biofuels and biochemicals. The high demand for fuel ethanol has driven academia and industry to investigate ethanol production using the most abundant nonfood plant resource - lignocellulosic biomass. While scientists and engineers are still searching for viable methods to convert all the biomass components to value-added fuels, they also realize that, as in a refinery, the co-products can add significant value to the primary products (fuels) being produced from the biomass. Lignin takes up to 30% of the mass of lignincellulosics and has not found viable value-added applications. In addition, some natural chemicals from biorefinery processes have the potential for value-added high performance polymer products but are currently underutilized. For example, the tall oil, a byproduct from the Kraft pulp process, mainly consists of rosin and fatty acids and both are important feedstock chemicals. Capturing the values of co-products of biorefinery and maximizing their industrial utilizations will greatly enhance the economic competiveness of lignocellulosic biomass-to-ethanol conversion. Some agricultural residues which are polymer or polymer mixtures in nature, for example, soy meal and sugar beet pulp, could be valuable feedstocks for polymer materials but are currently underutilized. We anticipate that the proposed research will promote the following outcomes: (1) developing technologies using biorefinery coproducts and agricultural residues for new biobased polymers and polymer materials; (2) identifying and implementing renewable feedstock chemicals for polymer applications; (3) increasing penetration of biobased polymer materials into the coating industry, engineering polymers and home products.
Animal Health Component
(N/A)
Research Effort Categories
Basic
(N/A)
Applied
(N/A)
Developmental
(N/A)
Classification

Knowledge Area (KA)Subject of Investigation (SOI)Field of Science (FOS)Percent
5111820202050%
5110612202050%
Knowledge Area
511 - New and Improved Non-Food Products and Processes;

Subject Of Investigation
0612 - Conifer forests of the West; 1820 - Soybean;

Field Of Science
2020 - Engineering;
Goals / Objectives
The objectives of this project are: (1) to synthesize various novel polymers using rosin acid and lignin-derived monomers, etc, as feedstock chemicals; (2) to explore new polymer applications using renewable feedstock and agricultural residues; (3) to expand the spectrum of properties of biobased polymer materials by investigating the structure-composition-property relationship. We anticipate that the proposed research will promote the following outcomes: (1) developing technologies using biorefinery coproducts and agricultural residues for new biobased polymers and polymer materials; (2) identifying and implementing renewable feedstock chemicals for polymer applications; (3) increasing penetration of biobased polymer materials into the coating industry, engineering polymers and home products.
Project Methods
Currently, biobased polymers cannot compete with the performance and variety of conventional polymers. Aromatic and cycloaliphatic monomers (or building blocks) bring molecular rigidity and thermal stability to polymers and therefore are the most important feedstock chemicals for high performance engineering polymers. However, engineering polymers rely entirely on petrochemical feedstocks. Rosin acids and lignin-derived phenolic chemicals are rigid chemicals from renewable resources because they all possess cyclic molecular structure. In addition, they all have functional groups which are polymerizable or can be converted to polymerizable groups. In this project, the PI will utilize rosin acids and lignin-derived phenolic chemicals as feedstock chemicals for polymer synthesis. Our approach is to use rosin derivatives and lignin-derived chemicals to replace or partially replace petrochemical aromatic or cycloaliphatic monomers in preparations of various polymers. Particularly, engineering plastics including epoxies, polyurethane, and polyethers are to be prepared using these new feedstock chemicals. Although being similar in molecular rigidity, the characteristics of rosin acid and lignin-derived chemicals still differ significantly from that of conventional aromatic and cyclic compounds. Therefore, designs of the monomer and the polymer molecular structures will be manipulated to compare with or simulate that of the petroleum-based counterparts. Furthermore, the spectrum of properties of the new polymers will be detected and the possible range of applications will be defined. Soy flour (SF) and sugar beet pulp (SBP) are mainly used for low value animal feeds. In this project, novel use of agricultural residues for polymeric materials will be investigated. Chemical modification of soy flour for use as a superabsorbent will be conducted by reactive extrusion. Sugar beet pulp contains a significant amount of pectin which is a water soluble polymer. In the presence of sufficient water, pectin possesses the thermoplastic-like flowability under shear, which can be used to prepare SBP-based plastics and to blend SBP as a plastic component with other polymers.

Progress 01/01/12 to 12/31/17

Outputs
Target Audience:Specific target audiences included attendees at a number of international professional conferences that draw large audiences from the chemical, polymers and plastics industries. The research results were presented in a series of invited presentations. Additionally, research results were shared with the polymer chemistry scientific community and industry in a number of peer-reviewed journal articles and book chapters. Our research has received significant attention as reflected in the continuously growing citations of our papers by peer researchers, with a total citations of 4600+ times according to Google Scholars. In addition, we also often receive emails and phone inquiries from companies who have some interest in our research. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?Over years, we have trained a number of NARA sure students, REU interns, and graduate dtudents. How have the results been disseminated to communities of interest?We have a ttended many technilca conferences. Some of the results have been reported in public media. What do you plan to do during the next reporting period to accomplish the goals? Nothing Reported

Impacts
What was accomplished under these goals? Biorefinery refers to the industrial process/operation for production of energy and chemicals using biomass instead of petroleum oil. Depending on the specific biorefinery process, the main coproducts vary from lignin of the lignocellulosic biorefinery, distiller's dried grains with solubles (DDGS) of corn ethanol, to glycerol and soy protein (other seed proteins) from biodiesels, etc. These coproducts are generally underutilized and some are even disposed of as waste. As awareness of sustainability development is spreading into every industry and has aroused the conscience of the general public, bioproducts which are produced from renewable feedstocks are the ultimate solution and the investigation of the production technology is urgently needed. As natural chemicals and polymers have long been used as feedstocks for the productions of various specialty products in industry, coproducts and agricultural residues, which resemble those renewable feedstocks in chemical structures and physical performance, are not well-utilized but potentially important resources for industrial products. The long-term goal of my research is to develop various viable preparation technologies for biobased polymer materials products. My group has been investigating utilization of biorefinery coproducts, agricultural residues and renewable chemicals and polymers in general for biobased polymer materials. Our biobased polymer research is multidirectional, covering all the major aspects - synthesis, processing, applications and even recycling. First, the feedstock used in our investigation are diverse, it includes not only the coproducts, agricultural residues, waste cooking oil, but also the general renewable chemicals and polymers. Second, we always try to practice the principles of green chemistry in the preparations of biobased polymer materials in terms of simple reaction or preparation procedure, mild reaction conditions, aqueous or solvent-free reaction, etc. We have also made a great effort to explore applications for the existing commercial biobased polymers and for our new biobased polymer materials. The following specific accomplishments were achieved: 1. Synthesized various novel polymers using rosin acid and lignin-derived monomers, etc., as feedstock chemicals; Our effort under this objective is focused on preparation of bioepoxies, and rosin, eugenol, dipentene, cinnamic acid, vegetable oil (including waste cooking oil) and lignin all have been used as renewable feedstocks. In addition, preparations of hydrogels, alternative unsaturated polyesters and polyurethanes are also explored by using renewable feedstocks. Our efforts were further expanded into the syntheses of biobased compounds such as camphor-derived liquid crystals and vegetable oil-derived PVC stabilizers and plasticizers. Particularly, we have introduced several innovations to the synthesis and preparation methods. Vegetable oil derived acrylic compounds are traditionally prepared by reacting acrylic acid and epoxidized oil. We introduced a novel direct acrylation method by reacting the oil with vegetable oil, eliminating the epoxidized oil intermediate. This method not only simplify the reaction process but also lead to better acrylated product. The acrylated oil prepared by our method has no free hydroxyl groups. Another important innovation is the introduction of redox initiation system in the grating modification of PLA. Compared to the free simple radical initiation system, redox initiation gives higher conversion and higher degree of grafting. This finding is very important for grafting modification of polymers. PLA toughening is the most studied subject in PLA applications. We made a great contribution to PLA toughening by identifying the toughening mechanism and developed several new toughening methods. Notably, we introduced the first supertough ternary PLA blend through reactive compounding. We have introduced a macromonomer approach in the preparation of soy protein based superabsorbent hydrogels. This method ensures a high conversion of the protein into the crosslinked network structure, and the resulting hydrogels exhibit significantly higher mechanical properties than the corresponding controls. 2. Explored new polymer applications using renewable feedstock and agricultural residues; With the developed new biobased polymer materials, in the past 5 years, we pursued the following applications: Polyester and epoxy powder coatings based on the rosin feedstock Soy protein-based superabsorbent hydrogels for soil moisture conditioning Vegetable oil-based novel epoxy for sporting goods Lignin and waste cooking oil derived epoxy for modification of asphalt Lignin-based absorbent for heavy metal ion Soy protein-based fiber, adhesives and composites Biopolymer/wood flour composites PVC stabilization and plasticization using rosin and vegetable oil-derived compounds 3. Expanded the spectrum of properties of biobased polymer materials by investigating the structure-composition-property relationship. Study of the structure-composition-property relationship runs through all of our materials research. We focused on the application of vitrimer chemistry in biobased epoxies. Different from the traditional epoxy chemistry, epoxy vitrimers exhibit self-healing, shape memory, and a certain levels of recyclability and reprocessibility. This work is the first one for biobased vitrimers and is expected to enlighten other biobased vitrimers thereafter. My group spearheaded several important advances for toughening and blending of polylactic acid (PLA). My group first revealed the toughening mechanism of PLA by elastomeric polymers and introduced a novel ternary PLA blend system by reactive compounding. We have also introduced a creative preparation method of PLA/soy protein blends by processing soy protein as a plastic component, which greatly improves the properties of the resulting PLA blends. This work has made significant impact to the industry of biobased polymer materials and the findings are important contributions to the knowledgebase of bioproducts.

Publications

  • Type: Other Status: Published Year Published: 2012 Citation: For the 5 years of the project, we have published 47 peer-reviewed journal papers, 6 book chapters. We have also given 21 invited presentations at national and international conferences. In addition, we have been awarded 4 U.S. Patents and have 7 more pending U.S. patents. These activities are detailed in progress reports submitted for the past 5 years.


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

Outputs
Target Audience:Specific target audiences included attendees at 4 international professional conferences that draw large audiences from the chemical, polymers and plastics industries. The research results were presented in 4 invited presentations and two regular presentations. Additionally, research results were shared with the polymer chemistry scientific community and industry in 11 peer-reviewed journal articles and one book chapter. Our research has received significant attention as reflected in the continuously growing citations of our papers by peer researchers, with yearly citations of 700+ times in 2017 according to Google Scholars. In addition, we also often receive emails and phone inquiries from companies who have some interest in our research. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?Two NARA SURE undergraduate interns and an REU studentwere trained under this project. 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? For the past year, my research investigation is a step along the continuum of my long-term research goal, developing various viable preparation technologies for biobased polymer materials products. Besides applications of plant protein, rosin and lignin coproducts for polymer materials, my investigation also covers the utilizations of vegetable oils including waste cooking oils and production of sugar-derived biochemicals. Furthermore, my investigation has expanded into the recycling of cotton waste and carbon fiber reinforced epoxy composites in an attempt to address the sustainability of polymer materials in a broader scope. In summary, we have published 11 journal papers, filed 4 invention disclosures and had one patent application granted, and attended three international conferences in 2017. It should be stressed that our technological inventions of hempseed oil-derived epoxy and chemical recycling of epoxy composite wastes were successfully licensed to two companies, respectively. The following specific accomplishments were achieved: 1). Synthesized various novel polymers using rosin acid and lignin-derived monomers, etc., as feedstock chemicals; For the past year, we have made an impressive progress on a new structure design of biobased polymers and innovation of preparation methods. Specifically, we have made the following contributions to the advance of biobased polymers. We introduced the first biobased vitrimer epoxy material which was based on the eugenol feedstock. The synthesis method and properties of the vitrimer materials were studied in detail, and some of the results were published in a paper in Macromolecules (listed in journal publications #1). Vitrimers are emerging as a new type of crosslinked polymers which are based on dynamic crosslinking and are developed to address the recyclability and reprocessiblity of thermosets. All the investigations were on petroleum-based polymer systems until we introduced the first biobased polymer vitrimer system. This effort maylead a new wave of investigations on biobased vitrimers. We also introduced a novel triazole-containing lignin-based absorbent for heavy metal ions. The click chemistry method was employed to ensure high conversion of the lignin modification. The results were published in a paper in ACS Sustainable Chemistry and Engineering (publication #4). This research is the first of its kind using the triazole moiety for high selective absorption for Cd (II) ions, and exhibited clear high absorptions than other lignin-derived absorbents. We introduced a novel macro-monomer method for the preparation of soy protein hydrogels. The alkali-treated soy protein was introduced with the methacrylate groups, so the resulting modified soy protein acted as a macro-crosslinker in the hydrogel synthesis. The results were published in a paper (#8). The macro-monomer approach ensures the high incorporation of protein into the crosslinked network structure of the gel, improving the overall performance. This method sets a new framework for future synthesis of protein-based hydrogels. Another study completed improving grafting efficiency of PLA. We compared steric hindrance effects of the monomer and redox initiation on the grafting efficiency. It has been found the steric hindrance is the determining factor and the addition of reductant greatly improves the grafting degree but also accelerates the degradation of PLA. The findings were published in publication #5. This study addresses the long standing low grafting efficiency problem of polymers, and provides a useful guideline for future investigative effort. We have made a significant effort to investigate mild chemical recycling methods for epoxy composites. We have obtained a significant understanding of the effects of the catalyst, reaction medium, and reaction conditions on degradation of the epoxy resin. The results have been published in two papers (#3 & 6). We have developed creative methods for degrading the epoxies using benign catalysts in aqueous medium and mild reaction temperature. This research has received great interest from industry and one company has licensed our inventions. 2). Explored new polymer applications using renewable feedstock and agricultural residues; In the past year, the following related applications were pursued. Use of vegetable oil-derived zinc salts as PVC stabilizer; zinc and calcium salts of tung oil fatty acid derived polycarboxylic acid were prepared and used as a PVC thermal stabilizer. The results indicates these new Zn/Ca salts are superior to the traditional Zn/Ca stearate salts in stabilizing PVC during processing. One paper was published (#10). Lignin-based absorbents for absorption of heavy metal ions. The lignin-based absorbent containing the triazole group exhibit high selectivity for Ca+2 ions and is superior to other lignin-based absorbents in the literature. One paper was published (#4). The better performance of our lignin-based absorbent is probably due to the multiple nitrogen atoms in the product. Investigation of potential uses of lignin and soy protein-based hydrogels for soil moisture conditioning: The biodegradability of the hydrogels based on both lignin and soy protein are examined and proved. Owing to their biodegradability, they are more appropriate and beneficiary for agricultural applications. Utilization of sunflower head residue for composite materials: Sunflower head residue is usually thrown away. We investigated its utilization as filler for polymers. The results suggests it can be used as a cheaper filler to replace the woody one and provide comparable properties. One paper was published (#11). 3). Expanded the spectrum of properties of biobased polymer materials by investigating the structure-composition-property relationship. Study of the structure-composition-property relationship runs through all of our materials research. We started to explore the application of vitrimer chemistry in biobased epoxies last year. Eugenol was turned into an epoxy compound which was then cured with an anhydride. Different from the traditional epoxy chemistry, epoxy vitrimers exhibit self-healing, shape memory, and a certain levels of recyclability and reprocessibility. This work is the first one for biobased vitrimers and is expected to enlighten other biobased vitrimers thereafter. One paper has been published (#1).

Publications

  • Type: Journal Articles Status: Published Year Published: 2017 Citation: 1. Tuan Liu, Cheng Hao, Liwei Wang, Yuzhan Li, Wangcheng Liu, Junna Xin, Jinwen Zhang.* Eugenol-derived Biobased Epoxy: Shape Memory, Repairing and Recyclability, Macromolecules 2017, 50, 8588  8597 (DOI: 10.1021/acs.macromol.7b01889) 2. Yaping Li; Zhijun Xu; Shuyan Liu; Jinwen Zhang, and Xiaoning Yang.* Molecular simulation of reverse osmosis for heavy metal ions using functionalized nanoporous graphenes, Computational Materials Science 2017, 139, 65  74. (http://dx.doi.org/10.1016/j.commatsci.2017.07.032) 3. Tuan Liu; Xiaolong Guo; Wangcheng Liu; Cheng Hao; Liwei Wang; William C. Hiscox; Chengyun Liu; Can Jin; Junna Xin; Jinwen Zhang.* Selective cleavage of ester linkages of anhydride-cured epoxy using a benign method and reuse of the decomposed polymer in new epoxy preparation, Green Chemistry, 2017, 19, 4364  4372 (DOI: 10.1039/C7GC01737E). 4. Can Jin; Xueyan Zhang; Junna Xin; Guifeng Liu; Guomin Wu; Zhenwu Kong;* Jinwen Zhang.* Clickable synthesis of 1,2,4-triazole modified lignin-based adsorbent for the selective removal of Cd(II); ACS Sustainable Chemistry and Engineering 2017, 5, 4086  4093 (10.1021/acssuschemeng.7b00072) 5. Wangcheng Liu; Tao Liu; Tuan Liu; Tian Liu; Junna Xin; Hang Liu; Linshu Liu; Jinwen Zhang.* Improving grafting efficiency of dicarboxylic anhydride monomer on polylactic acid by manipulating monomer structure and using co-monomer and reducing agent, Industrial & Engineering Chemistry Research 2017, 56, 3020  3927 (10.1021/acs.iecr.6b05051) 6. Tuan Liu; Meng Zhang; Xiaolong Guo; Chengyun Liu; Tian Liu; Junna Xin; Jinwen Zhang.* Mild chemical recycling of aerospace fiber/epoxy composite wastes and utilization of the decomposed resin; Polymer Degradation and Stability 2017, 137, 20  27. (10.1016/j.polymdegradstab.2017.03.017) 7. Mahshid Maroufkhani; AliAsghar Katbab;* Wangcheng Liu; Jinwen Zhang.* Polylactide (PLA) and Acrylonitrile Butadiene Rubber (NBR) blends: The effect of ACN Content on Morphology, Compatibility and Mechanical Properties, Polymer 2017, 115, 37  44 (http://dx.doi.org/10.1016/j.polymer.2017.03.025) 8. Wenjia Song; Junna Xin; Jinwen Zhang.* One-pot Synthesis of Soy Protein (SP)-Poly(acrylic acid) (PAA) Superabsorbent Hydrogels via Facile Preparation of SP Macromonomer, Industrial Crops & Products 2017, 100, 117  125. (http://dx.doi.org/10.1016/j.indcrop.2017.02.018) 9. Xiaoxu Teng; Hui Xu; Jianwei Shi; Junna Xin; Jinwen Zhang.* Preparation and properties of hydrogels based on PEGylated lignosulfonate amine, ACS Omega 2017, 2, 251  259. (DOI: 10.1021/acsomega.6b00296) 10. Mei Li; Jinwen Zhang; Junna Xin; Kun Huang; Shouhai Li; Mei Wang; Jianling Xia. Design of green zinc-based thermal stabilizers derived from tung oil fatty acid and study of thermal stabilization for PVC, Journal of Applied Polymer Science 2017, DOI:10.1002/app.44679 11. Wangcheng Liu; Tian Liu; Hang Liu; Junna Xin; Jinwen Zhang*, Zayniddin Kamarovich Muhidinov, Linshu Liu.* Poly(butylene adipate-co-terephthalate) and sunflower head residue biocomposites, Journal of Applied Polymer Science 2017. DOI: 10.1002/app.44644
  • Type: Books Status: Published Year Published: 2017 Citation: 12. Feedstocks for the Preparation of Polyurethane Polymers, in Sustainable Polymers from Biomass, Chuanbing Tang and Chang Y Ryu (eds). Chapter 5, pp. 91 -101.Wiley-VCH Verlag GmbH & Co. KGaA 2017.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2017 Citation: 1. Developing diverse polymer applications for the lignin feedstock (final paper number: POLY 715), in symposium "Advances in Lignin: Chemicals, Polymers & Materials", Division of Polymer Chemistry, 254th ACS National Meeting in Washington, DC, August 20-24, 2017. 2. Vegetable oil-based thermosets: Molecule design for higher performance (final paper number: POLY 630), in symposium "Green Polymer Chemistry: Biobased Materials & Biocatalysis", Division of Polymer Chemistry, 254th ACS National Meeting in Washington, DC, August 20-24, 2017. 3. Investigation of superabsorbent hydrogels based on renewable feedstocks: alternative crosslinking method and potential applications, 24th Annual Meeting of the BioEnvironmental Polymer Society, September 20 - 22, 2017. 4. Utilization of lignin as feedstock for various polymer applications, (Junna Xin) 24th Annual Meeting of the BioEnvironmental Polymer Society, September 20 - 22, 2017. 5. A novel biobased vitrimer based on a eugeno-derived epoxy, (Tuan Liu) 24th Annual Meeting of the BioEnvironmental Polymer Society, September 20 - 22, 2017. 6. Superabsorbent hydrogels from reneable feedstocks: Alternative crosslinking methods and potential applications, 2017 International Technology and Application Conference on Bio-based Materials, April 20 - 21, Ningbo, China


Progress 10/01/15 to 09/30/16

Outputs
Target Audience:Specific target audiences included attendees at several professional conferences. The research results were presented in a plenary speech and three invited talks at national and international conferences that draw large audiences from the chemical, polymers and plastics industries. Additionally, research results were shared with the polymer chemistry scientific community and industry in 4 peer-reviewed journal articles. Our research has received significant attention as reflected in the continuously growing citations of our papers by peer researchers, with yearly citations over 400 times since 2012 according to Google Scholars. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?All the graduate students and postdocs have received various hand-on trainings in conducting experiments and were mentoredin experimental design from the PIs on the projects. In addition, 2 summer undergraduate interns were trained on a NIFA project in 2016. How have the results been disseminated to communities of interest?In 2016, my group published 1 book chapter and 6 papers in peer-reviewed journals including top quality polymer journals. In addition, we also have 2 U.S. patents granted. WSURF has also filed a new provisional patent application for my research findings on vegetable oil epoxies. The research results were presented in a Keynote lecture "Broadening the Properties and Application Windows of Biobased Polymers" by myself at: 14th International Symposium on Bioplastics, Biocomposites & Biorefining, May 31 - June 3, 2016, Guelph, Canada. In addition, 1 oral presentation was given by my student, Xiaojie Guo, at 2016 American Physical Society meeting in Baltimore, MD: "Mechanochemical modification of lignin and application of the modified lignin for thermoplastics and thermosets" What do you plan to do during the next reporting period to accomplish the goals?I will continue the research by further manipulating the design of molecular structure of the renewable polymers to tailor application performance and explore the potential applications.

Impacts
What was accomplished under these goals? We have made important progress towards diversifying feedstocks and broadening the spectrum of biobased polymer materials. First, we extended our investigation of lignin utilization into new areas including epoxy asphalt and hydrogels. Lignin-derived epoxies in combination with curing agents derived from other renewable resources constitute a complete biobased epoxy resin system. It is a novel approach to prepare new epoxy asphalts for performance binders. We also developed a novel lignin amine approach to modify and crosslink lignin in hydrogel preparation. Four lignin-related papers based on the results were published in 2016 and more will be coming in 2017. Our research of soy protein-based hydrogel has achieved important results. The resulting hydrogels proved to be advantageous in water saving and promoting plant growth when applied as a soil water conditioner. This research has raised a lot of attention from the industry. We have made significant progress in converting sugar-derived 1,2-propylene glycol to acrylonitrile. This research is a very important contribution to the biorefinery industry and carbon fiber industry. Our novel grafting modification for PLA set up a framework for future practice in academic research and industry to produce functional polymers by melt free radical grafting reaction. We also made impressive progress in utilizing the recycled chemicals from carbon fiber composites. This study may potentially provide great economic advantages to the advanced composites industry.

Publications

  • Type: Book Chapters Status: Accepted Year Published: 2017 Citation: Meng Zhang, Yonghong Zhou, and Jinwen Zhang. Use of Rosin and Turpentine as Feedstocks for the Preparation of Polyurethane Polymers, in Sustainable Polymers from Biomass, Chuanbing Tang and Chang Y Ryu (eds). Chapter 5, pp. 91 -101.Wiley-VCH Verlag GmbH & Co. KGaA 2017.
  • Type: Journal Articles Status: Published Year Published: 2016 Citation: Mei Li; Jinwen Zhang; Junna Xin; Kun Huang; Shouhai Li; Mei Wang; Jianling Xia. Design of green zinc-based thermal stabilizers derived from tung oil fatty acid and study of thermal stabilization for PVC, Journal of Applied Polymer Science 2016, DOI:10.1002/app.44679
  • Type: Journal Articles Status: Published Year Published: 2016 Citation: Wangcheng Liu; Tian Liu; Hang Liu; Junna Xin; Jinwen Zhang*, Zayniddin Kamarovich Muhidinov, Linshu Liu.* Poly(butylene adipate-co-terephthalate) and sunflower head residue biocomposites, Journal of Applied Polymer Science 2016. DOI: 10.1002/app.44644
  • Type: Journal Articles Status: Published Year Published: 2016 Citation: Junna Xin; Pei Zhang; Michael P. Wolcott; Jinwen Zhang.* A novel and formaldehyde-free preparation method for lignin amine and its enhancement for soy protein adhesive, Journal of Polymers and the Environment 2016, 10.1007/s10924-016-0844-x.
  • Type: Journal Articles Status: Published Year Published: 2016 Citation: Xiaojie Guo; Xin Junna; Jinwen Zhang.* Mechanochemical oleation of lignin through ball milling and properties of its blends with PLA, Chemistry Select 2016, 1, 3449  3454. DOI: 10.1002/slct.201600633.
  • Type: Journal Articles Status: Published Year Published: 2016 Citation: Ruoshui Ma; Mond Guo; Melissa Quintero; Vincent R. Hebert; Jinwen Zhang; Karthikeyan K. Ramasamy; Xiao Zhang.* Peracetic Acid Depolymerization of Biorefinery Lignin for Production of Selective Monomeric Phenolic Compounds, Chemistry - A European Journal, 2016, 22, 10884  10891 (DOI: 10.1002/chem.201600546).
  • Type: Journal Articles Status: Published Year Published: 2016 Citation: Junna Xin; Mei Li; Michael P. Wolcott; Jinwen Zhang.* A green epoxy resin system based on lignin and tung oil and its application in epoxy asphalt, ACS Sustainable Chemistry and Engineering 2016, 4, 2754 - 2761 (DOI: 10.1021/acssuschemeng.6b00256).


Progress 10/01/14 to 09/30/15

Outputs
Target Audience:Specific target audiences included attendees at several professional conferences. The research results were presented in a plenary speech and three invited talks at national and international conferences that draw large audiences from the chemical, polymers and plastics industries. Additionally, research results were shared with the polymer chemistry scientific community and industry in 4 peer-reviewed journal articles. Our research has received significant attention as reflected in the continuously growing citations of our papers by peer researchers, with an average citations above 400 times in recent 3 years according to Google Scholars. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?All the graduate students and postdocs have received various hand-on trainings in conducting experiments and mentoring on experiment designs from the PIs on the projects. How have the results been disseminated to communities of interest?In 2015, my group published four (4) papers in peer-reviewed journals including the top quality polymer journals. In addition, we also have one patent granted. WSURF has also filed a new full patent application for my research findings on sop protein-based hydrogels. The research results were presented in a Plenary talk by myself at: 1. Plenary lecture: New Perspectives of Vegetable Oils as Feedstocks for High Performance Polymers, 13th Brazilian Congress of Polymers, Natal, Brazil, Oct. 18 - 22, 2015. and three invited presentations by myself and Dr. Xin at: 2. Broadening the Property and Application Windows of Biobased Polymers by Diversifying Building Blocks, 2015 Pacific Polymer Conference, Kauai, HI, December 9 - 13, 2015. 3. Manipulation of molecular design of vegetable oil-based polymers for high performance, 2015 Pacific Chemistry Conference, Oahu, HI, December 14 - 20, 2015. 4. Performance enhancement of lignin-based thermosets and polymer blends, 2015 Metabolic Engineering and Green Manufacturing in Microorganisms, July 8 -11, 2015, Beijing, China. What do you plan to do during the next reporting period to accomplish the goals?I will continue the research by further manipulating the design of molecular structures of the renewable polymers to tailor application performance and explore the potential applications. ?

Impacts
What was accomplished under these goals? We made important progress towards diversifying feedstocks and broadening the spectrum of biobased polymer materials. First, we extended our investigation of lignin utilization into new areas including epoxy asphalt and hydrogels. Lignin-derived epoxies in combination with curing agents derived from other renewable resources constitute a totally biobased epoxy resin system. It is a novel approach to prepare new epoxy asphalts for performance binders. We also developed a new approach to modify and crosslink lignin in hydrogel preparation. Several papers based on the results will be published in 2016. Another important progress in utilization of renewable chemicals is the rosin-based powder coating resin. With the financial support from the NSF/IUCRC Center of Bioplastics and Biocomposites, we developed rosin-based curing agents for polyester type and polyester-epoxy hybrid type powder coatings. Our rosin-base powder coating curing agents were evaluated by an industrial partner and determined to be very promising. Our research of soy protein-based hydrogel has achieved important results. The synthesis has been optimized and the gel content can achieve 80 % or higher. We have also established an HPLC method for analysis of residual monomers. The resulting hydrogels proved to be advantageous in water saving and promoting plant growth when applied as soil water conditioner. In addition, we introduced a novel method for grafting modification of PLA and other renewable polymers. This method is expected to provide a more efficient and more economical method than current methods in the literature. We also made progress in utilizing the recycled chemicals from carbon fiber composites. This study may potentially provide great economic advantages to the advanced composites industry. jQuery18306951885936483724_1453838622354

Publications

  • Type: Journal Articles Status: Published Year Published: 2015 Citation: Jia Cheng; Pei Zhang; Tao Liu; Jinwen Zhang.* Preparation and properties of hydrogels based on PEG and isosorbide building blocks with phosphate linkages, Polymer 2015, 78, 212  218 (dx.doi..org/10.1016/j.polymer.2015.10.009)
  • Type: Journal Articles Status: Published Year Published: 2015 Citation: Kun Huang, Zengshe Liu,* Jinwen Zhang,* Shouhai Li, Mei Li, Jianling Xia, Yonghong Zhou. A self-crosslinking thermosetting monomer with both epoxy and anhydride groups derived from tung oil fatty acids: synthesis and properties, European Polymer Journal 2015, 70, 45 - 54. (doi: 10.1016/j.eurpolymj.2015.06.027)
  • Type: Journal Articles Status: Published Year Published: 2015 Citation: Xiaojie Guo; Jinwen Zhang;* Jijun Huang.* Poly(lactic acid)/polyoxymethylene blends: Morphology, crystallization, rheology, and thermal mechanical properties, Polymer 2015, 69, 103  109 (DOI: 10.1016/j.polymer.2015.05.050)
  • Type: Journal Articles Status: Published Year Published: 2015 Citation: Meng Zhang, Zhenyang Luo, Jinwen Zhang,*, Shuigen Chen, Yonghong Zhou.* Effect of novel phosphorus-nitrogen flame retardant on rosin-based rigid polyurethane foams, Polymer Degradation and Stability 2015, 120, 427  434. (dx.doi.org/10.1016/j.polymdegradstab.2015.08.001)


Progress 10/01/13 to 09/30/14

Outputs
Target Audience: Specific target audiences included attendeesat several professional conferences. The research results were presented in 2 keynote talks and one invited talk at national and international conferences, which draw a large audience from chemical, polymers and plastics industries. Additionally, research results were shared with the polymer chemistry scientific community and industry in 15 peer-reviewed journal articles and one book chapter. It is worth mentioning that our research has received significant attentions as it is reflected in the continuously growing citations of papers by peer researchers everywhere. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided? All the graduate students, Wenjia Song, Jia Cheng, Kun Huang and Yu Fu, Mei Li, have received various hand-son trainings in conducting experiments and mentoring of experiment designs from the postdocs working in this project. How have the results been disseminated to communities of interest? In 2013, my group published fifteen (15) papers in peer-reviewed journals including top quality journals such as Polymer, BioMacromoleces, ACS Applied Materials and Interface and Bioresource technology. In addition, we also published a book chapter in an ACS symposium. WSURF has filed two (2) new provisional patent applications on my research findings. The research results were presented in two (2) keynote talks by myself at: 1) the 2014 BioEnvironmental Polymer Society Meeting in Kansas City, MO (Oct.14-17, 2014); 2) 13th International Symposium on Bioplastics, Biocomposites & Biorefining in Guelph, Canada (May 19 - 24, 2014); and one invited presentation: 3) at the symposium of Green Polymer Chemistry: Biobased Materials and Biocatalysis at the 248rd ACS National Meeting, August 10 - 14, 2014, San Francisco, CA What do you plan to do during the next reporting period to accomplish the goals? I will continue the research by further manipulating the design of molecular structures of the renewable polymers to tailor application performance and explore the potential applications.

Impacts
What was accomplished under these goals? We have made important progress towards diversifying feedstock and broadening the spectrum of biobased polymer materials. First, we introduced the concept of using partially depolymerized lignin for the preparation of novel thermoset resins and accordingly developed two depolymerization methods for partially depolymerized lignin (PDL): base-catalyzed depolymerization in super critical solvent and mild hydrogenolysis under the catalysis of Raney Nickel. Both reactions are performed under mild reaction conditions. We demonstrated that theuse of lignin in the PDL form for thermoset application exhibited much improved performance over theuse of lignin in its high molecular weight form. Now, we are further looking for other eco-friendly and economically viable functionalization methods for lignin. Because many rosin derivatives are solid and are not very convenient in resin application, we are exploring the synthesis of fatty acid-based epoxies and curing agents, which are low viscosity liquids. When rosin-derived and fatty acid-derived resins are used together in the same systems, they exhibit complementary effects and offer overall improved properties for the cured resins. Furthermore, we have demonstrated that eugenol and dipentiene can be turned to liquid epoxies and curing agents are effective alternatives to the petroleum-based counterparts. Another creative development is the introduction of vegetable oil-based PVC stabilizers. Mixed Ca/Zn PVC stabilizers based on vegetable oils have proven to stabilize PVC equally or even better than the conventional counter parts, and have the additional advantages of improved mixing and no toxicity. Soy protein is a hydrophilic natural polymer and is abundantly available in the US. Turning it into a superabsorbent is a highly attractive endeavor because it will enable the production of high-volume products to be made from renewable resources. The results, to date, indicate that the graft polymerization of partially hydrolyzed soy proteins is very promising. Furthermore, a novel approach is introduced in the preparation of the graft polymers, which offers a great degree of control of design of structure. The plant growth test has shown promising results. We have obtained extensive experience on PLA toughening, PLA blends with other polymers and PLA composites with agricultural residues and nano-sized filler reinforcements. Now we will move forward with our interest in developing new functional methods for PLA and other polymers. We first introduced the use of the redox initiation system in melt grafting of acrylic monomers onto polyolefins and the grafting efficiency is greatly increased over the traditional peroxide initiators. This is of great interest to both industry and academia because functional PLA and other polymers have a lot of applications. In addition, we introduced a novel method for the preparation of functionalized graphene: ionic liquid-assisted exfoliation of graphite oxide for simultaneous reduction and functionalization to graphenes with improved properties. This method is expected to provide a more efficient and more economic method than current methods found in the literature.

Publications

  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Jianglei Qin; Michael Wolcott; Jinwen Zhang. 2014. Use of polycarboxylic acid derived from partially depolymerized lignin as curing agent for epoxy application, ACS Sustainable Chemistry & Engineering 2, 188  193.
  • Type: Book Chapters Status: Published Year Published: 2014 Citation: Junna Xin, Pei Zhang, Kun Huang and Jinwen Zhang. Developing Vegetable Oil-Based High Performance Thermosetting Resins, in Soy-Based Chemicals and Materials; Brentin; Chapter 13, pp. 299  313, ACS Symposium Series; American Chemical Society: Washington, DC, 2014.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Pei Zhang; Junna Xin; Jinwen Zhang. 2014. Effects of catalyst type and reaction parameters on one-step acrylation of soybean oil, ACS Sustainable Chemistry & Engineering 2, 181  187.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Jianglei Qin; Hongzhi Liu; Pei Zhang; Michael Wolcott; Jinwen Zhang. 2014. Use of eugenol and rosin as feedstock for biobased epoxy resins and study of curing and performance properties, Polymer International 63, 760  765.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Shifeng Deng; Jia Cheng; Xiaojie Guo; Long Jiang; Jinwen Zhang. 2014. Fiber spinning of polyacrylonitrile grafted soy protein in an ionic liquid/DMSO mixture solvent, Journal of Polymer and the Environment 22, 17  26.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Mei Li; Jinwen Zhang; Kun Huang; Shouhai Li; Jianchun Jiang; Jianling Xia. 2014. Mixed Calcium and zinc salts of dicarboxylic acids derived from rosin and dipentene: Preparation and thermal stabilization for PVC, RSC Advances 4(108), 63576  63585.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Yu Fu; Linshu Liu; Jinwen Zhang; William C. Hiscox. 2014. Tailoring the Properties of Polylactic acid/Graphene Nanocomposites through Graphene Functionalization and epoxy-containing elastomer Interface Modifier, Polymer 55, 6381  6389.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Meng Zhang; Jinwen Zhang; Yonghong Zhou. 2014. Synthesis and fire properties of rigid polyurethane foams made from a polyol derived from melamine and cardanol, Polymer Degradation and Stability 110, 27-34.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Yu Fu; Linshu Liu; Jinwen Zhang. 2014. Manipulating Dispersion and Distribution of Graphene in PLA through Novel Interface Engineering for Improved Conductive Properties, ACS Applied Materials and Interface 6, 14069 - 14075.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Xiaojie Guo; Hongzhi Liu; Jijun Huang; Jinwen Zhang. 2014. Effects of polyoxymethylene as a polymeric nucleating agent on isothermal crystallization and visible transmittance of poly(lactic acid), Industrial & Engineering Chemistry Research 53, 16754 - 16762.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Jianchun Jiang; Jinwen Zhang; Xiaohua Yang; Yan Zhang; Shouhai Li; Jian Song; Kun Huang; Jianling Xia. 2014. Preparation of a new liquid thermal stabilizer from rosin and tung oil and properties of the stabilized PVC, Polymer Degradation and Stability 109, 129  136.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Gustavo F. Brito; Junna Xin; Pei Zhang; Tom�s J. A. M�lo; Jinwen Zhang. 2014. Enhanced melt free radical grafting efficiency of polyethylene using a redox initiation method, RSC Advances 4, 2642526433.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Xiaoping Rao; Jinwen Zhang; Jianqiang Zheng; Zhanqian Song; Shibin Shang. 2014. Chiral ionic liquid crystals with a bulky rigid core from renewable camphorsulfonic acid, RSC Advances 4, 2533425340.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Kun Huang; Zengshe Liu; Jinwen Zhang; Shouhai Li; Mei Li; Jianling Xia; Yonghong Zhou. 2014. Epoxy monomers derived from tung oil fatty acids and its regulable thermosets cured in two synergistic ways, BioMacromolecules 15, 837  843.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Junna Xin; Pei Zhang; Michael Wolcott; Xiao Zhang; Jinwen Zhang. 2014. Partial depolymerization of enzymolysis lignin via mild hydrogenolysis over Raney Nickel, Bioresource Technology 155, 422  426.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Junna Xin; Pei Zhang; Kun Huang; Jinwen Zhang. 2014. Study of green epoxy resins derived from renewable cinnamic acid and dipentene: Synthesis, curing and properties, RSC Advances 4 (17), 8525  8532.


Progress 01/01/13 to 09/30/13

Outputs
Target Audience: Specific target audiences included attendees to several professional conferences. The research results were presentedat three(3) invited oral presentations: at the 2013 American Institute of Chemical Engineers (AIChE) annual meeting, San Francisco, Nov. 6-8 2013; Use of lignin as feedstock for epoxy application, 2013 International Wood Composite Symposium, Seattle, WA, April 3-4, 2013; 1st International Biobased Macromolecule Materials Forum (Ningbo, China, Nov. 13-14, 2013). In addition, my student Jiang Cheng,and my postdocs Pei Zhang and Junna Xin gave oral and poster presentations at the 245th ACS National Meeting (Indianapolis, IN, September, 2013). Additionally, research results were shared with the polymer chemistry scientific community and industryin 10 articles in the following publications: Bioresource Technology, ACS Sustainable Chemistry & Engineering, Polymer International, Green Chemistry, Journal of Polymer and the Environment, Industrial Crops & Products, Industrial & Engineering Chemistry Research, Green Materials and the Journal of Material Chemistry. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided? Allfour graduate students, Wenjia Song, Jia Cheng, Kun Huang and Yu Fu, have received various hand-on trainings in conducting experiments and mentoring on experiment designs from the three postdocs working on this project. How have the results been disseminated to communities of interest? Research results were presentedat three(3) invited oral presentations: at the 2013 American Institute of Chemical Engineers (AIChE) annual meeting, San Francisco, Nov. 6-8 2013; Use of lignin as feedstock for epoxy application, 2013 International Wood Composite Symposium, Seattle, WA, April 3-4, 2013; 1st International Biobased Macromolecule Materials Forum (Ningbo, China, Nov. 13-14, 2013). In addition, my student Jiang Cheng, and my postdocs Pei Zhang and Junna Xin gave oral and poster presentations at the 245th ACS National Meeting (Indianapolis, IN, September, 2013). Additionally, research results were shared with the polymer chemistry scientific community and industryin 10 articles in the following publications: Bioresource Technology, ACS Sustainable Chemistry & Engineering, Polymer International, Green Chemistry, Journal of Polymer and the Environment, Industrial Crops & Products, Industrial & Engineering Chemistry Research, Green Materials and the Journal of Material Chemistry. What do you plan to do during the next reporting period to accomplish the goals? Continueto investigate the preparation of new thermosetting polymers from rosin, terpene, lignin, vegetable oils, and other natural chemical feedstocks and to study the properties of the resulting resins. Continue theinvestigations of the synthesis and properties of superabsorbents using soy protein. Continue theinvestigations on PLA toughening and polymer blends based on agricultural residues such as soy protein concentrate.

Impacts
What was accomplished under these goals? As usual, in the past year, we have made a continuous effort to investigate the preparation of new thermosetting polymers from rosin, terpene, lignin, vegetable oils, and other natural chemical feedstocks and to study the properties of the resulting resins. We have also made in-depth investigations of the synthesis and properties of superabsorbents using soy protein. Furthermore, we have conducted additional investigations on PLA toughening and polymer blends based on agricultural residues such as soy protein concentrate. Specifically, we have advanced the investigation in the following aspects: 1. Thermosetting resins from renewable feedstocks - developing lignin depolymerization technology and lignin-based epoxies - developing epoxies and curing agents using rosin, dipentiene and other natural chemicals; - developing plant oil- and fatty acid-derived epoxies and curing agents. 2. Soy protein-based superabsorbents - effects of hydrolysis of soy protein on water absorption capacity; - reaction parameters on soy protein on water absorption capacity; - rheological and mechanical properties. 3. Other biobased polymer materials - mechanism of PLA reactive toughening; - developing soy protein polymer blends; - developing novel functionalization method of graphene and PLA/graphene composites. Outcomes and impact We have made important progress towards diversifying feedstock and broadening the spectrum of biobased polymer materials. First, we introduced the concept of using partially depolymerized lignin for the preparation of novel thermoset resins. Accordingly, we have creatively developed two depolymerization methods for partially depolymerized lignin (PDL): base-catalyzed depolymerization in super critical solvent and mild hydrogenolysis under the catalysis of Rane Nickel, both of which are performed under mild reaction conditions. Furthermore, the resulting PDL was turned into polycarboxylic acid which was used as a curing agent for epoxies. Use of lignin in the PDL form for thermoset application exhibited much improved performance than use of lignin in its high molecular weight form. Earlier, we demonstrated the use of rosin as feedstock for glycidyl ester type epoxies, and anhydride and amide type curing agents. Because many rosin derivatives are solid and are not very convenient in resin application, we are exploring the synthesis of fatty acid-based epoxies and curing agents which are low viscosity liquids. When rosin-derived and fatty acid-derived resins are used together in the same systems, they exhibit complementary effects and offer overall improved properties for the cured resins. Furthermore, we have demonstrated that eugenol and dipentiene can be turned to liquid epoxies and curing agents are effective alternatives to the petroleum-based counterparts. Soy protein is a hydrophilic natural polymer and turning it into a superabsorbent is a highly attractive endeavor because it will enable the production of the high volume products to be made from renewable resources. The results to date indicate that the graft polymerization of partially hydrolyzed soy proteins is very promising. Furthermore, a novel macromonomer approach is introduced in the preparation of the graft polymers, which offers a great degree of control of design of structure and eliminates the need for crosslinkers. The reactive toughening of PLA via a ternary blend system was further studied. The blending temperature and degree of neutralization and degree of functionalization of the zinc ionomer modifier was found to greatly influence the impact strength of the blends. In addition, we introduced a novel method for the preparation of functionalized graphene: ionic liquid-assisted exfoliation of graphite oxide for simultaneous reduction and functionalization to graphenes with improved properties. This method is expected to provide a more efficient and more economic method than current methods in the literature.

Publications

  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Junna Xin, Pei Zhang, Kun Huang, Jinwen Zhang. Study of green epoxy resins derived from renewable cinnamic acid and dipentene: Synthesis, curing and properties, Bioresource Technology, doi: http://dx.doi.org/10.1016/j.biortech.2013.12.092
  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Jianglei Qin; Michael Wolcott; Jinwen Zhang. Use of polycarboxylic acid derived from partially depolymerized lignin as curing agent for epoxy application, ACS Sustainable Chemistry & Engineering 2013, DOI: dx.doi.org/10.1021/sc400227v
  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Jianglei Qin; Hongzhi Liu; Pei Zhang; Michael Wolcott; Jinwen Zhang. Use of eugenol and rosin as feedstock for biobased epoxy resins and study of curing and performance properties, Polymer International 2013, DOI:10.1002/pi.4588
  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Kun Huang; Pei Zhang; Jinwen Zhang; Shouhai Li; Jianling Xia; Yonghong Zhou. Preparation of biobased epoxies using tung oil fatty acid-derived C21 diacid and C22 triacid and study of properties, Green Chemistry 2013, 15, 2466  2475.
  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Scott Anderson; Jinwen Zhang; Michael Wolcott. Effect of Interfacial Modifiers on Mechanical and Physical Properties of the PHB Composite with High Wood Flour Content, Journal of Polymer and the Environment 2013, 21, 631  639.
  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Kun Huang; Jinwen Zhang; Mei Li; Jianling Xia; Yonghong Zhou. Exploration of the complementary properties of biobased epoxies derived from rosin diacid and dimerized fatty acid for balanced performance, Industrial Crops & Products 2013, 49, 497  506.
  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Hongzhi Liu; Xiaojie Guo; Wenjia Song; Jinwen Zhang. Effects of Metal Ion Type on Ionomer-Assisted Reactive PLA Toughening, Industrial & Engineering Chemistry Research 2013, 52, 4787  4793.
  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Pei Zhang; Jinwen Zhang. One-step acrylation of soybean oil (SO) for the preparation of SO-based macromonomers, Green Chemistry 2013, 15, 641-645. (doi: 10.1039/c3gc36961d)
  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Bo Liu; Gabriel Z. Guevara; Jinwen Zhang; Linshu Liu. Performance Enhancement of Poly(lactic acid)/Soy Protein Concentrate Blends by Promoting Formation of Network Structure, Green Materials 2013, 1, 176 - 185. (doi: 10.1680/gmat.12.00015)
  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Yu Fu; Jinwen Zhang; Hang Liu; William C. Hiscox; Yi Gu. Ionic liquid-assisted exfoliation of graphite oxide for simultaneous reduction and functionalization to graphenes with improved properties, Journal of Material Chemistry A 2013, 1, 2663  2674. (doi: 10.1039/C2TA00353H)
  • Type: Theses/Dissertations Status: Published Year Published: 2013 Citation: Yu Fu. Processing and Properties of Novel Graphene-Based PLA Bionanocomposites, Washington State University Libraries.


Progress 01/01/12 to 12/31/12

Outputs
OUTPUTS: During the past year, we have made significant effort to investigate the preparation of new thermosetting polymers from rosin, terpene, lignin, vegetable oils, and other natural chemical feedstocks and to study the properties of the resulting resins. In addition, we have explored the synthesis of superabsorbents using soy protein. Furthermore, we have conducted more in-depth investigations on polylactic acid (PLA) toughening and polymer blends based on agricultural residues such as soy protein concentrate and sugar beet pulp. Specifically, we have advanced the investigation of the following aspects: 1. Thermosetting resins from renewable feedstocks by developing rosin-derived epoxies; developing dipentene (terpene)-derived anhydride curing agents; developing fatty acid-derived epoxies and curing agents; 2. Soy protein-based superabsorbents were studied, specifically the effects of hydrolysis of soy protein on water absorption capacity; the reaction parameters on soy protein on water absorption capacity; 3. Other biobased polymer materials were studied including the mechanism of PLA reactive toughening; developing sugar beet pulp polymer blends; developing soy protein polymer blends. The research results were presented in four (4) invited oral presentations by myself at the 243th American Chemical Society (ACS) National Meeting (San Diego, CA, May. 25 -29, 2012), 2012 BioEnvironmental Polymer Society annual Meeting (Denton, TX, Sept. 18-21, 2012), 2012 Corn Utilization & Technology Conference (Indianapolis, IN, June 4-6, 2012); 1st International Symposium on Polymer Ecomaterials (Changchun, China, Aug. 19-23, 2012). In addition, my student Wenjia Song also gave an oral presentation at the Society of Plastic Engineers (SPE) meeting (May 2012) in Seattle and at the 244th ACS National Meeting (Aug. 2012) in Philadelphia, respectively. PARTICIPANTS: Dr. Jinwen Zhang (PI), oversaw the project, directly advised his graduate students and postdocs who participated in different aspects of the project. Dr. Hongzhi Liu, postdoc, focused on the development of polymer materials including characterizations and processing; Dr. Pei Zhang, postdoc, focused on synthesis of new polymers using rosin, vegetable oil and other renewable feedstocks; Dr. Jianglei Qin, postdoc, focused on investigation of depolymerization of lignin and synthesis of epoxy resins using lignin; Wenjia Song, PhD student, focused on preparation of superabsorbents using soy protein; Jia Cheng, PhD student, worked on developing new type epoxy resins; Kun Huang, visiting student, worked on developing rosin and vegetable oil-based epoxies; Rui Zhu, MS student (graduated), mainly undertook the study of soy protein/PLA blends; Bo Liu, PhD student (graduated), mainly undertook the study of foaming processing technology. Feng Chen, PhD student (graduated), mainly undertook the study of Soy protein polymer blends. TARGET AUDIENCES: U.S. farmers in general will be the immediate beneficiaries of the investigation by finding new uses of agricultural and forest products and residues in a market dominated by petroleum-based polymers and plastics. The general public will benefit from the results, because the biobased polymers and natural polymers are environmentally friendly and renewable; and their products are biodegradable, compostable, or carbon-neutral after use. In addition, the findings from this project will advance the knowledge base of biobased polymers and bioplastics and stimulate future developments within the biobased polymer materials industry. PROJECT MODIFICATIONS: Not relevant to this project.

Impacts
Rosin acids have a fused ring structure and can be converted into glycidyl ester type epoxies and anhydride or amide type curing agents. The resulting resins also possess comparable properties to that of bisphenol A type epoxy resins. However, many rosin derivatives are solid and are not very convenient in epoxy application. Furthermore, like many other bisphenol A type epoxies, rosin based epoxies are also brittle. To address these problems, we have begun to explore the synthesis of fatty acid-based epoxies and curing agents which are low viscosity liquids. The preliminary results indicated fatty acid-derived epoxy or curing agent not only helped to dissolve rosin-derived counterparts but also flexibilized the cured resin. Terpene is a natural liquid chemical exudated with rosin from pines. We also studied the functionalization of terpene and turned it into an anhydride, which is a liquid of low viscosity which can dissolve the solid rosin anhydride. Soy protein is a hydrophilic natural polymer and turning it into a superabsorbent is a highly attractive endeavor because it will enable the production of the high volume products to be made from renewable resources. We have shown it is very promising by the graft polymerization of partially hydrolyzed soy proteins. More in-depth investigation is underway. Furthermore, we have made more important progress towards our long-term objective of developing biobased polymer materials, which covers a broad range of blends and composites. Specifically, our research on thermoplastic sugar beet pulp plastics, soy protein plastics, and PLA toughening have received significant attention from peers.

Publications

  • Bo Liu; Jinwen Zhang; Linshu Liu; Arland T. Hotchkiss. Utilization of pectin extracted sugar beet pulp for composite application, Journal of Biobased Materials and Bioenergy 2012, 6, 185-192.
  • Rui Zhu; Hongzhi Liu; Jinwen Zhang. Effects of functionality and concentration of maleated poly(lactic acid) (PLA) on morphology and properties of PLA/soy protein composites, Industrial & Engineering Chemistry Research 2012, 51, 7786-7792(http://dx.doi.org/10.1021/ie300118x).
  • Weili Li; David R. Coffin; Tony Z. Jin; Nicolas Latona; Cheng-Kung Liu; Bo Liu; Jinwen Zhang; LinShu Liu. Biodegradable composites from polyester and sugar beet pulp with antimicrobial coating for food packaging, Journal of Applied Polymer Science 2012, 126, E361-E372.DOI: 10.1002/app.36885.
  • Wenjia Song; Hongzhi Liu; Feng Chen; Jinwen Zhang. Effects of ionomer characteristics on reactions and properties of poly(lactic acid) ternary blends prepared by reactive blending, Polymer 2012, 53, 2476-2484. (doi: 10.1016/j.polymer.2012.03.050)
  • Hongzhi Liu; Li Guo; Xiaojie Guo; Jinwen Zhang. Effects of reactive blending temperature on impact toughness of poly(lactic acid) ternary blends, Polymer 2012, 53, 272-276. (dio:10.1016/j.polymer.2011.12.036)
  • Elvie E. Brown; Marie-Pierre Laborie; Jinwen Zhang. Glutaraldehyde treatment of bacterial cellulose/fibrin composites: impact on morphology, tensile and viscoelastic properties, Cellulose 2012, 19, 127-137.
  • Jinwen Zhang (editor and author). Rosin-based Chemicals and Polymers, iSmithers Rapra Publishing 2012, ISBN: 9781847355041
  • Kun Huang; Mei Li; Shouhai Li; Jianling Xia; Jinwen Zhang. Plant Oil-Based Curing Agents for Epoxies, in Degradable Polymers and Materials: Principles and Practice (2nd Edition); Khemani, K., et al.; Chapter 14, pp. 225-234, ACS Symposium Series; American Chemical Society: Washington, DC, 2012.
  • Long Jiang; Jinwen Zhang. Biodegradable polymers and polymer blends, in Handbook of Biopolymers and Biodegradable Plastics (ISBN: 978-1-4557-2834-3), Sina Ebnesajjad, Chapter 6, pp. 109-128, Elsevier 2012.
  • Hongzhi Liu; Jinwen Zhang. Toughening Modification of Poly(lactic acid) via Melt Blending, In Biobased Monomers, Polymers, and Materials; Smith, P., et al.; chapter 3, pp. 27-46, ACS Symposium Series; American Chemical Society: Washington, DC, 2012.
  • Feng Chen; Jinwen Zhang. Processing Soy Protein Concentrate as Plastic in Polymer Blends. In Polymer Science: A Comprehensive Reference; Matyjaszewski K and Moller M (eds.) Vol. 10, chapter 14, pp. 249-254. Amsterdam: Elsevier BV, 2012.