The Development of New Coating and Adhesive Systems Derived from Novel Plant Oil-Based Polymers

THE DEVELOPMENT OF NEW COATING AND ADHESIVE SYSTEMS DERIVED FROM NOVEL PLANT OIL-BASED POLYMERS

Sponsoring Institution

National Institute of Food and Agriculture

Project Status

TERMINATED

Funding Source

OTHER GRANTS

Reporting Frequency

Annual

Accession No.

0227969

Grant No.

2012-38202-19283

Project No.

ND05498

Proposal No.

2011-06243

Multistate No.

(N/A)

Program Code

MM.2

Project Start Date

Feb 15, 2012

Project End Date

Feb 14, 2015

Grant Year

2012

Project Director
Chisholm, B.

Recipient Organization
NORTH DAKOTA STATE UNIV
(N/A)
FARGO,ND 58105

Performing Department
Center for Nanoscale Science and Engineering

Non Technical Summary
Non-Technical Summary At present, organic chemicals are almost entirely derived from building blocks that are obtained from natural gas, petroleum, and coal. Approximately 13 percent of the crude oil used in the United States currently goes into the production of nonfuel chemicals. Since fossil resources are limited, there is an ongoing need to develop useful chemicals from renewable resources. Renewable resources that have been used to produce chemicals include plant oils, polysaccharides, sugars, and wood. Of these, plant oils are the most important renewable raw materials for the chemical industry. Chemicals derived from plant oils have been used to produce surfactants, components for cosmetics, lubricants, polymers, coatings, and flooring materials. A primary drawback associated with the use of plant oil-based materials for many coating applications is their significantly lower thermomechanical properties compared to petrochemical-based materials. The proposal team recently developed a break-through technology involving the synthesis of novel plant oil-based vinyl ether monomers and the subsequent controlled polymerization of the monomers to produce high molecular weight polymers. Using soybean oil (SBO) as the plant oil, it was demonstrated that replacement SBO or SBO derivatives with the novel, high molecular weight polymer derived from SBO dramatically decreased cure time and increased thermomechanical properties of a variety of coating systems. A powerful synthetic tool used extensively in essentially all industries that utilize polymeric building blocks is copolymerization. A major attribute associated with the polymer technology developed by the proposal team is that copolymerization can be used to tailor properties to a specific application. Thus, the primary objective of the proposed project is to utilize copolymerization to tailor properties with primary emphasis being the enhancement of mechanical and thermomechanical properties to enable the replacement of a much larger fraction of petrochemical-based polymers and oligomers than can be accomplished with current plant oil-based technology. To facilitate transition of the technology to industry, five major coating manufacturers have reviewed the proposal team's background technology and indicated their willingness to provide consultation and potentially evaluate promising copolymers resulting from the project. A Life Cycle Analysis will be conducted to demonstrate the environmental advantages of the most promising copolymer composition over a commercially available petrochemical analog.

Animal Health Component

(N/A)

Research Effort Categories

Basic

(N/A)

Applied

100%

Developmental

(N/A)

Classification

Knowledge Area (KA)	Subject of Investigation (SOI)	Field of Science (FOS)	Percent
511	1899	2000	100%

Knowledge Area
511 - New and Improved Non-Food Products and Processes;

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

Field Of Science
2000 - Chemistry;

Keywords

cationic polymerization

Goals / Objectives
Goals/Objectives/Expected Outputs The objectives of the proposed research are to: 1) utilize our novel monomer and polymer synthesis technology to develop an array of plant oil-based polymers for different segments of the coatings and adhesive markets with emphasis being placed on the utilization of copolymerization to tailor properties and enhance performance; 2) demonstrate the utility of the optimized plant oil-based polymers for different segments of the coatings and adhesives markets by comparing the properties of coating and adhesives formulated with the new polymers to commercially validated petroleum-based coatings provided by the industrial partners interested in this technology; 3) dissemination of the results of the project to industry through publication, patenting, and presentations; 4) scale-up of the most promising polymer compositions to the 500 g. scale for sampling to interested coating manufacturers; and 5) completion of a LCA to understand the environmental advantages associated with the plant oil-based polymers. The short-term goal for the project is the generation of the data and polymer samples to facilitate the adoption of this polymer technology by members of the coatings and adhesives industry such that they utilize their own resources to commercialize the technology. The long-term goal for the proposed project is to support commercialization of this polymer technology in the coatings and adhesives industries and, in general, to expand the use of plant oil-based materials by providing new building blocks with properties that were previously unobtainable. Technical questions that will be answered by conducting the proposed research are as follows: 1. What advantages can be obtained from copolymerization in terms of coating performance and reduction in VOCs 2. What segments of the coatings market will benefit the most from this new polymer technology 3. What are the major new attributes provided by these new plant oil-based polymers over current, commercially available plant oil-based raw materials 4. What is the potential for these new plant oil-based polymers to displace petroleum-based building block for coatings and adhesives 5. What are the environmental benefits of these plant oil-based polymers over petroleum-based polymers used in the coatings and adhesives industries

Project Methods
Methods The project plan for the proposed two year project has been logically organized into three different phases. The first phase of the project, which will be conducted over the course of 12 months, will focus on the synthesis and characterization of an array of plant oil-based polymers. Monomer synthesis will be achieved using base-catalyzed transesterification of the plant oil with (2-vinyoxy)ethanol. Polymerization will be achieved using carbocationic polymerization. Since a major limitation that has prevented plant oils from being widely utilized in coatings is their inherently low thermomechanical properties, emphasis will be placed on greatly enhancing thermomechanical properties by copolymerization of the plant oil-based monomers with monomers that will provide rigidity to the polymer backbone. Polymer characterization will involve methods that assess both the composition of the polymers produced as well as their basic thermal, rheological, and physical properties. The second phase, which will be conducted over a period of 10 months, will largely focus on a demonstration of the utility of the novel copolymers in coatings and adhesives using select formulations based on different market segments such as radiation-cure, polyurethanes, epoxies, and waterborne architectural coatings. Material formulations for demonstrating the utility will be developed with input from the companies that have agreed to provide support as indicated by the Letters of Support submitted with the proposal. Material performance data will be generated using industry standard methods such as those described by the American Society for Testing and Materials. The third phase, which will be conducted over a period of 4 months, will involve a Life Cycle Analysis conducted by a recognized industry expert and scale-up of the most promising copolymer compositions for sampling to the industrial contributors. In addition to sampling the industrial contributors with promising polymers, data generated as a result of the project will also be shared to obtain feedback with respect to the commercial utility of the polymers.

Progress 02/15/12 to 02/14/15

Outputs
Target Audience: The target audience for this project includes: -scientists working in the area of materials derived from plant oils - companies interested in commercializing new polymers and polymeric materials derived from renewable resources, specifically plant oils -farmers that produce oil seed crops students interested in learning about the conversion of plant oils to polymeric materials Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided? This project has resulted in tremendous interest from industry. In fact, the patent pending technology is in the process of being transferred to a start-up company, Renuvix LLC. In addition, the results of the project have been utilized to secure multiple other related research grants from multiple agencies including NSF, DOE, and the United Soybean Board. As a result, the PI for the project has gained extensive experience in technology commercialization. Further a tremendous number of presentations and publications have been generated that has greatly enhanced the career development for the PI as well as for the graduate students and post-docs that have worked on the project. How have the results been disseminated to communities of interest? A tremendous number of publications and presentations have been produced from the project. Many of the presentations include invited presentations. Also, a great deal of interest has been expressed by industry and multiple samples and presentations have been provided to different companies. What do you plan to do during the next reporting period to accomplish the goals? Nothing Reported

Impacts
What was accomplished under these goals? - Several different comonomers were copolymerized with 2-(vinyloxy)ethyl soyate (2-VOES) as a means to increase the glass transition temperature of cured coatings where curing was achieved via autoxidation. The results of the studies showed that copolymerization with the appropriate monomer enables coatings that quickly become dry-to-touch and develop good solvent resistance. Compared to long oil alkyd resins, these copolymers dry much faster, are lower in color, and possess better chemical resistance. - By distilling 2-VOES prior to polymerizing, water-white polymers can be produced that give colorless, highly transparent coatings that cure by autoxidation. The PI for the project was contacted by a company that makes oil-based paints for artists that are primarily just dispersions of pigments in linseed oil. There are several issues with these traditional oil-based artist paints which include high yellowness derived from linseed oil, long drying/curing times, and embrittle over long periods of time. As a result of this knowledge, white paints were produced using poly(2-VOES) as the binder and the color and drying time compared to an analogous linseed oil paint. The results showed that the use of poly(2-VOES) in place of linseed oil provided dramatically better color and dramatically lower drying/curing time. - The most promising copolymer identified for coating applications was based on 2-VOES and maleic anhydride (MA). These copolymers provide coatings that are dry-to-the-touch as soon as the solvent is evaporated and the chemical resistance is developed very fast. As a result, these coatings have a high probability of displacing coventional alkyd resins in coatings. As a result, a life cycle assessment was conducted through a subcontract to OminTech International in which the environmental impact of a 2-VOES/MA copolymer was compared to data previously generated for an long oil alkyd. The results of the assessment showed that the 2-VOES/MA coolymer has a signficantly lower environmental impact than the long oil alkyd. - 2-VOES was copolymerized with a poly(ethylene glycol) (PEG) vinyl ether monomer to produce amphiphilic copolymers. These copolymers could be dispersed in water to form stable emulsions without the need for surfactant. By simply adding a water-based drier package, clear coatings were produced from the aqueous polymer dispersions that cured relatively quickly by autoxidation and showed excellent optical clarity. These soybean oil-based amphiphilic copolymers were also shown to be surface active and funding from the United Soybean Board was obtained to investigate them as polymeric, non-ionic surfactants in model shampoo formulations. The results obtained from this additional project have been very exciting.

Publications

Type: Book Chapters Status: Published Year Published: 2014 Citation: H. Kalita, S. Alam, D. Kalita, A. Chernykh, I. Tarnavchyk, J. Bahr, S. Samanta, A. Jayasooriyama, S. Fernando, S. Selvakumar, A. Popadyuk, D. S. Wickramaratne, M. Sibi, A. Voronov, A. Bezbaruah, and B. J. Chisholm, "Synthesis and characterization of novel soybean oil-based polymers and their applications in coatings cured by autoxidation," ACS Symposium Series, vol. 1178, Soy-Based Chemicals and Materials, chapter 16, 371-390 (2014).
Type: Conference Papers and Presentations Status: Published Year Published: 2014 Citation: H. Kalita, S. Alam, D. Kalita, A. Chernykh, I. Tarnavchyk, J. Bahr, S. Samanta, A.Jayasooriyama, S. Fernando, S. Selvakumar,D. Suranga Wickramaratne, M. Sibi,and B. J. Chisholm, Novel biobased polymers for coatings applications, European Coatings Conference Biobased Materials for Industrial Coatings, Dusseldorf, Germany, Dec. 8-9, 2014.
Type: Conference Papers and Presentations Status: Published Year Published: 2015 Citation: B. J. Chisholm, H. Kalita, D. Kalita, S. Alam, A. Chernykh, I. Tarnavchyk, J. Bahr, S. Samanta, A. Jayasooriyama, S. Fernando, S. Selvakumar, D. Suranga Wickramaratne,and M. Sibi, "Novel Bio-based Polymers for Coating Applications," Proceedings for The Waterborne Symposium, Feb. 9-13 in New Orleans, LA, 2015
Type: Journal Articles Status: Awaiting Publication Year Published: 2015 Citation: H. Kalita, S. Alam, D. Kalita, A. Jayasooriyamu, S. Fernando, S. Samanta, J. Bahr, S. Selvakumar, M. Sibi, J. Vold, C. Ulven, and B. J. Chisholm, "Novel Alkyd-Type Coating Resins Produced Using Cationic Polymerization," Journal of Coatings Technology and Research, in press, 2015
Type: Journal Articles Status: Published Year Published: 2014 Citation: A. Popadyuk, H. Kalita, B. J. Chisholm, and A. Voronov, "Evaluation of soy-based surface active copolymers as surfactant ingredients in model shampoo formulations," International journal of cosmetic science, vol. 36, 537-545 (2014)

Progress 02/15/13 to 02/14/14

Outputs
Target Audience: The target audience was researchers and product developers working in the coatings industry. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided? Multiple post-docs and graduate students have worked on different aspects of the project, which has been instrumental in there development as scientists. In addition, the PI has been invited to give multiple presentations on this research, which has help with his career development. In addition, multiple companies have become interested in the technology and samples have been provided. These interactions with industry have helped develop the PIs professional network. Finally, other grants have been obtained from agencies outside of the USDA to further support this research. How have the results been disseminated to communities of interest? Yes. Multiple publications and presentations have been made. What do you plan to do during the next reporting period to accomplish the goals? Most of the funds for research have been spent. The primary effort is being focused on the Life Cycle Analysis, which largely involves the subcontractor, OminiTech International.

Impacts
What was accomplished under these goals? A significant amout of emphasis was placed on copolymerization of the plant oil vinyl ether monomers to enhance properties. Three different series of copolymers were produced using three different comonomers. Three different comonomers were menthol vinyl ether (MVE), cyclohexyl vinyl ether (CHVE), and maleic anhydride (MA). From each series of polymers, coatings were prepared and characterized using autoxidation as the curing mechanism. For MVE and CHVE, coating properties were highly dependent on comonomer concentration in the polymer as well as curing conditions. The results obtained with MVE were published in Green Chemistry and the results for the CHVE coatings were published as a proceeding for the American Coatings Conference. The proceeding will be submitted to the Journal of Coatings Technology and Research for wider dissemenation of the results. For the polymers and coatings based on MA as the comonomer, coatings with very high modulus and glass transition temperature were produced. These results will be written-up into a publication manuscript and a patent application may also be filed. Palm oil was used as a starting material to produce poly(vinyl ether)s to demonstrate the converting a plant oil with a relatively low degree of unsaturation can be used to produce useful coatings. The palm oil-based poly(vinyl ether)s were converted to polyols and used to produce novel polyurethane coatings. These results were written up in a manuscript that has been accepted for publication in the Journal of Palm Oil Research. The concept used for making polymers from plant oils was also used to produce poly(vinyl ether)s from cardanol, which is derived from cashew nut oil. Coatings based on these polymers were found to rapidly cure by autoxidation and possesses very good properties. The results will be disseminated via a publication manuscript in the near future. The plant oil-bases polymer technology that is the basis for the project is being licensed by a start-up company, Renuvix LLC, for future commercialization. An LCA is in progress and the results will accompany the final report.

Publications

Type: Journal Articles Status: Published Year Published: 2014 Citation: H. Kalita, S. Selvakumar, a. Jayasooriya, S. Fernando, S. Samanta, J. Bahr, S. Alam, M. Sibi, J. Vold, C. Ulven, and B. J. Chisholm, Bio-based poly(vinyl ether)s and their application as alkyd-type surface coatings, Green Chem., 16, 1974-1986 (2014).
Type: Journal Articles Status: Published Year Published: 2014 Citation: S. Alam, H. Kalita, A. Jayasooriya, S. Samanta, J. Bahr, A. Chernykh, M. Weisz, and B. J. Chisholm, 2-(Vinyloxy)ethyl soyate as a versatile platform chemical for coatings: An overview, Eur. J. Lipid Sci. Technol., 116, 2-15 (2014).
Type: Conference Papers and Presentations Status: Published Year Published: 2014 Citation: H. Kalita, S. Alam, A. Jayasooriyamu, S. Fernando, S. Samanta, J. Bahr, S. Selvakumar, M. Sibi, J. Vold, C. Ulven, and B. J. Chisholm, "Novel alkyd-type coating resins produced using cationic polymerization," presentation made at the American Oil Chemists Society Meeting that took place May 5-7, 2014 in San Antonio TX.
Type: Conference Papers and Presentations Status: Published Year Published: 2014 Citation: S. Alam, H. Kalita, A. Jayasooriya, A. Chernykh, S. Samanta, J. Bahr, and B. J. Chisholm, "Bio-based polyvinyl ethers for coating applications," Invited presentation made to the Cleveland Coatings Society on March 20, 2014 in Cleveland, OH.
Type: Conference Papers and Presentations Status: Published Year Published: 2013 Citation: H. Kalita, A. Jayasooriyamu, S. Fernando, and B. J. Chisholm, "Novel high molecular weight polymers based on palm oil," Invited presentation made at the PIPOC conference on November 20, 2013 in Kuala Lumpur, Malaysian.
Type: Journal Articles Status: Accepted Year Published: 2014 Citation: H. Kalita, A. Jayasooriyamu, S. Fernando, and B. J. Chisholm, "Novel high molecular weight polymers based on palm oil," Journal of Oil Palm Research, In press
Type: Conference Papers and Presentations Status: Published Year Published: 2014 Citation: H. Kalita, S. Alam, A. Jayasooriyamu, S. Fernando, S. Samanta, J. Bahr, S. Selvakumar, M. Sibi, J. Vold, C. Ulven, and B. J. Chisholm, "Novel alkyd-type coating resins produced using cationic polymerization," proceedings for the American Coatings Conference that took place April 7-9, 2014 in Atlanta GA.

Progress 02/15/12 to 02/14/13

Outputs
Target Audience: The target audience for this project includes: - scientists working in the area of materials derived from plant oils - companies interested in commercializing new polymers and polymeric materials derived from renewable resources, specifically plant oils - farmers that produce oil seed crops - students interested in learning about the conversion of plant oils to polymeric materials Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided? • A number of research staff, post-docs, graduate students, and undergraduate students have worked on different aspects of the project. Since a number of people are contributing to the project, there has been tremendous opportunity for groups members to share their knowledge gained from the project with each other. In addition, the team approach has definitely increased efficiency and productivity on the project. • The success of the project has results in multiple invited presentations, which has made a significant impact on the PI's career. How have the results been disseminated to communities of interest? • 12 conference presentations were made on various aspects of the project. Due to the high impact results obtained from our research, several of the conference presentations have been invited presentations, which have included reimbursement of travel expenses by the host. • A publication recently came out in Green Chemistry and other manuscripts are in preparation • As a result of conference presentations, multiple companies are now interested in the technology. So far, we provided polymer samples to two different companies. What do you plan to do during the next reporting period to accomplish the goals? • We have a considerable amount of data that needs to be assembled into publication manuscripts. • Once we have assembled the new data, we will present the data to appropriate companies to get feedback on appropriate petroleum-based coatings to use as benchmarks for comparison purposes. • Recent results suggest that copolymers produced by conventional free radical polymerization have the highest commericialization potential. As a result, we will be putting more emphasis on copolymers derived from free radical polymerization. • Based on our results and company feedback, we will select polymer compositions to use for LCA.

Impacts
What was accomplished under these goals? • A number of copolymers were produced to improve thermal properties, specifically polymer glass transition temperature. The copolymers were used to produce coatings that were cured by either auto-oxidation or cationic photo-cure. The properties of coatings produced using these copolymers were characterized and the data are being compiled in the form of a manuscript for publication. • Copolymers were produced to impart water-dispersibility. The copolymers were found to be surface active and waterborne coating systems could be produced that did not require the use of a surfactant. The unsaturation derived from the soybean vinyl ether monomer enabled crosslinking of amphiphilic copolymers. The copolymers were also evaluated for potential application as non-ionic surfactants. • Novel copolymers were produced using conventional free radical polymerization. A company that sells products into the coatings and packaging markets have evaluated multiple samples of a specific copolymer produced using free radical polymerization. We recently supplied them with 5 lbs of polymer for extensive evaluation in their laboratories. • Investigations were carried out to enhance the commericial viability of the produciton of the plant oil-based vinyl ether polymers using cationic polymerization. The results of these investigations showed that living polymerization can be achieved at room temperature as opposed to the sub-ambient temperatures initially utilized. In addition, the polymerization process was modified such the time required to obtain essentially complete monomer conversion was reduced from 10 hours to less than 1 hour. Also, it was shown the amount of Lewis acid required to obtain polymerization could be reduced by a factor of four. • In order to widely disminate the results obtained and to generate interest from industry, 12 conference presentations were made on various aspects of the project. Due to the high impact results obtained from our research, several of the conference presentations have been invited presentations, which have included reimbursement of travel expenses by the host. • With regard to scale-up, we routinely have been preparing plant oil vinyl ether monomers on a scale that provides approximately 1 kg of monomer per batch using a 10 liter reactor. In addition, the 10 liter reactor has been used multiple times to produce 1.2 kg batches of copolymer by free radical polymerization. For cationic polymerization, a 3 liter reactor system was installed that enables about 500 g of polymer to be produced by cationic polymerization.

Publications

Type: Conference Papers and Presentations Status: Published Year Published: 2012 Citation: Contributed presentation made at the 103rd AOCS Meeting & Expo in Long Beach, CA on April 29-May 2. The title of the presentation was "Novel high molecular weight polymer and coatings derived from soybean oil."
Type: Conference Papers and Presentations Status: Published Year Published: 2012 Citation: Contributed presentation made at the 103rd AOCS Meeting & Expo in Long Beach, CA on April 29-May 2. The title of the presentation was "Novel amphiphilic copolymers derived from soybean oil."
Type: Journal Articles Status: Published Year Published: 2013 Citation: A. Chernykh, S. Alam, A. Jayasooriya, J. Bahr, and B. J. Chisholm,"Living carbocationic polymerization of a vinyl ether monomer derived from soybean oil, 2-(vinyloxy)ethyl soyate," Green Chemistry, 2013, DOI: 10.1039/C3GC40605A
Type: Conference Papers and Presentations Status: Published Year Published: 2013 Citation: Invited presentation made at The 6th Workshop on Fats and Oils as Renewable Feedstock for the Chemical Industry held in Karlsruhe, Germany on March 17-21. The title of the presentation was "Novel high molecular weight vinyl ether polymers based on plant oils."
Type: Conference Papers and Presentations Status: Published Year Published: 2013 Citation: Invited presentation made at the 245th National Meeting of the American Chemical Society held in New Orleans, LA on April 7-11. The title of the presentation was "Novel polyvinylethers derived from plant oils."
Type: Conference Papers and Presentations Status: Published Year Published: 2013 Citation: Invited presentation made at the 245th National Meeting of the American Chemical Society held in New Orleans, LA on April 7-11. The title of the presentation was "Novel bio-based epoxy resins."
Type: Conference Papers and Presentations Status: Published Year Published: 2013 Citation: Contributed presentation made at the 245th National Meeting of the American Chemical Society held in New Orleans, LA on April 7-11. The title of the presentation was "Novel biodegradable soybean oil and ethylene glycol-based amphiphilic copolymers for the treatment of zerovalent iron nanoparticles."
Type: Conference Papers and Presentations Status: Published Year Published: 2013 Citation: Contributed presentation made at the CoatingsTech conference held in Chicago, IL on March 11-13. The title of the presentation was "Novel multifunctional bio-based polymers for coating applications."
Type: Conference Papers and Presentations Status: Published Year Published: 2013 Citation: Contributed proceeding and presentation made at the CoatingsTech conference held in Chicago, IL on March 11-13. The title of the proceeding and presentation was "Novel soybean oil-derived acrylates for UV-curable coatings."
Type: Conference Papers and Presentations Status: Published Year Published: 2013 Citation: Invited presentation made at the CoatingsTech conference held in Chicago, IL on March 11-13. The title of the presentation was "Bio-Based polyvinyl ethers for coating applications."
Type: Conference Papers and Presentations Status: Published Year Published: 2013 Citation: Contributed presentation made at the 104th AOCS Annual Meeting & Expo in Montreal, Quebec, Canada on April 28-May 1. The title of the presentation was "Novel soybean oil-derived acrylates for UV-curable coatings."
Type: Conference Papers and Presentations Status: Published Year Published: 2013 Citation: Contributed presentation made at the 104th AOCS Annual Meeting & Expo in Montreal, Quebec, Canada on April 28-May 1. The title of the presentation was "Novel high molecular weight plant oil copolymers."