Progress 09/15/07 to 09/14/10
Outputs
OUTPUTS: Key activities and accomplishments included: - Preparation of solvent-free aqueous dispersions based on emulsified sucrose ester resins. - Synthesis of novel grafted sucrose ester resins having fast drying properties and low VOC. - Synthesis of epoxidized sucrose ester resins and their crosslinking through cationic photopolymerization and with anhydrides. Properties far exceeded that obtained from epoxidized vegetable oils and modulus values of up to 1 GPa could be achieved. - Prepared and characterized acrylate epoxidized sucrose ester resins. - Prepared and characterized sucrose ester polyols. Dissemination of the outcomes of the the research work has involved presentations at several different conferences including National meetings of the American Chemical Society, AOCS, American Coatings Association. The presentations are listed below: Xiao Pan, Partha Sengupta, Dean C. Webster, "Epoxy-anhydride curing of epoxidized sucrose esters of fatty acids," PMSE Preprints, 2010, 103, 268-269. (Presented at the ACS National Meeting, Boston, Ma., August 21-26, 2010.) Thomas J. Nelson, Dean C. Webster, "Monomer-grafted sucrose ester resins," PMSE Preprints, 2010, 103, 406-407. (Presented at the ACS National Meeting, Boston, Ma., August 21-26, 2010.) Partha Sengupta, Xiao Pan, Thomas J. Nelson, Adlina Paramarta, Dean C. Webster, "Autoxidative drying characteristics of waterborne coatings from renewable resources, 101st American Oil Chemists' Society Annual Meeting, Phoenix, Az., May 16-19, 2010. Dean C. Webster, "Reducing the environmental impact of protective and functional coatings," American Chemical Society National Meeting, San Francisco, Ca., March 21-25, 2010. Invited. Partha Pratim Sengupta, Xiao Pan, Thomas J. Nelson, Adlina Paramarta, Dean C. Webster, "Cationic UV curing characteristics of epoxidized sucrose esters," PMSE Preprints, 2010, 102, 888-889. (Presented at the ACS National Meeting, San Francisco, Ca., March 21-25, 2010.) Xiao Pan, Thomas J, Nelson, Dean C. Webster, "Novel enamine formation (EF) and air-drying (AD) co-curable coating resins: miscible blends of sucrose esters," PMSE Preprints, 2010, 102, 759-760. (Presented at the ACS National Meeting, San Francisco, Ca., March 21-25, 2010.) Adlina Paramarta, Partha Sengupta, Dean C. Webster, "Waterborne Coating Systems from Sucrose Soyate," poster presentation at the 5th Annual ASBMB/ACS Undergraduate Research Symposium, Fargo, N.D., October 30-21, 2009. Partha Sengupta, Xiao Pan, Dean C. Webster, "Waterborne long oil alkyd for coating wood," poster presentation at FutureCoat! Chicago, Illinois, October 14-16, 2008. PARTICIPANTS: CoPI Dr. Dean C. Webster, Professor, has provided overall direction for the project. CoPI Dr. Stuart G. Croll, Professor, has provided overall direction for the project. Partha Sengupta, Postdoctoral Research Associate, was involved in preparing the aqueous dispersions of sucrose ester resins and evaluating rheological properties. Abhijit Jadhav, Postdoctoral Research Associate, has explored the synthesis of some novel derivatives of sucrose ester resins. Xiao Pan, Graduate Research Assistant, has conducted experiments to prepare sucrose esters of fatty acids. He has also introduced novel functional groups into the sucrose ester system. TJ Nelson, Graduate Research Assistant, is exploring the use of driers and the drying behavior of the sucrose esters of fatty acids and the synthesis of monomer grafted sucrose ester resins. Umesh Harkal, Graduate Research Assistant, carried out the synthesis and characterization of fatty acid modified glycidyl carbamate resins. Adlina Paramarta, Undergraduate Research Student, is assisting with coating formulation, synthesis of novel acrylated multifunctional resins. TARGET AUDIENCES: The paint and coatings industry, including suppliers. Biomaterial supply (farming and crop processing) industry. PROJECT MODIFICATIONS: A one-year no-cost extension was requested and granted.
Impacts
While biobased materials have been used in paints and coatings for centuries, these technologies have not kept up with the performance demands of today's coatings, nor have they been able to keep up with current environmental regulations regarding the evolution of volatile organic compounds (VOCs). This project was designed to address these issues by designing coating polymers based substantially on renewable resources, such as sugars and oils, which have very low levels of VOCs, and can be used in high performance coatings. By designing new high performance coating systems based on renewable resources, these coating systems have the potential to replace those based on petroleum derived chemistries, meet current demanding performance expectations, and also meet current environmental regulations. We have shown that sucrose ester resins of vegetable oils can be a useful starting material for a number of important technological advances. These have included emulsified waterborne coatings systems, grafted resins, and epoxidized sucrose esters. Crosslinking of the epoxidized sucrose ester resins has led to breakthrough properties which have not yet been observed in other vegetable oil based systems. The systems we are exploring have a number of environmental benefits. First, our compounds have very little content from petroleum-based sources; they are substantially made from bio-derived, renewable chemicals. Second, many of the systems we are exploring have very little organic solvent content and thus do not contribute to air pollution. Thus, we have a "green+green" approach to new materials for the coatings industry. A key aspect of the project has been the development of new intellectual property and its protection through the patenting process. Licensing of the technology developed to companies for the purpose of commercializing the technology will provide industry with new high performance sustainable products for a large number of applications. Invention Disclosures/Patent Applications "Novel enamine compounds and coatings therefrom," US Provisional Patent Application Filed 2/6/2010, Application number 61/302,119. "UV cured coatings from highly functional epoxy resins," US Provisional Patent Application Filed 2/6/2010, Application No. 61/302,124. "Novel air drying glycidyl carbamate (GC) coatings," Disclosed to NDSU Technology Transfer Office. "Novel UV-curable urethane acrylate," US Provisional Patent Application Filed 5/25/2010, Application number 61/348,125. "Thermosets from biobased materials," US Provisional Patent Application filed 6/16/2010, Application number 61/355,453. "Novel grafted resins," US Provisional Patent Application filed 6/16/2010, Application number 61/355,497. "Novel acrylate functional biobased resins and coatings therefrom," US Provisional Patent Application filed 6/16/2010, Application number 61/355,487. "Novel highly functional bio-based polyols and coatings therefrom," Disclosed to NDSU Technology Transfer Office.
Publications
- Pan, X., Nelson, T.J., Webster, D.C. 2010, "Novel biobased dual-cure coating system," Prog. Org. Coat., in press.
- Pan, X., Sengupta, P., Webster, D.C. 2010, "Novel biobased epoxy compounds: epoxidized sucrose esters of fatty acids," Green Chemistry, submitted.
- Sengupta, P., Pan, X., Nelson, T.J., Paramarta, A., Hinderliter, B., Croll, S.G., Webster, D.C. 2010, "Rheological study of dispersion stability of sucrose ester and drainage property of its coatings," manuscript in preparation.
- Sengupta, P., Pan, X., Nelson, T.J., Paramarta, A., Hinderliter, B., Webster, D.C. 2010, "Autoxidative drying characteristics of water dispersed vegetable oil sucrose ester resins," manuscript in preparation.
- Pan, X., Sengupta, P., Webster, D.C. 2010, "Epoxy-anhydride curing of epoxidized sucrose esters of fatty acids," PMSE Preprints, 103, 268-269. (Presented at the ACS National Meeting, Boston, Ma., August 21-26, 2010.)
- Nelson, T.J., Webster, D.C. 2010, "Monomer-grafted sucrose ester resins," PMSE Preprints, 103, 406-407. (Presented at the ACS National Meeting, Boston, Ma., August 21-26, 2010.)
- Sengupta, P., Pan, X., Nelson, T.J., Paramarta, A., Webster, D.C. 2010, "Cationic UV curing characteristics of epoxidized sucrose esters," PMSE Preprints, 102, 888-889. (Presented at the ACS National Meeting, San Francisco, Ca., March 21-25, 2010.)
- Pan, X., Nelson, T.J., Webster, D.C. 2010, "Novel enamine formation (EF) and air-drying (AD) co-curable coating resins: miscible blends of sucrose esters," PMSE Preprints, 102, 759-760. (Presented at the ACS National Meeting, San Francisco, Ca., March 21-25, 2010.)
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Progress 09/15/08 to 09/14/09
Outputs
OUTPUTS: Initiated in late 2007, the research work initially focused on the preparation and characterization of solvent-free aqueous dispersions of novel resins based on vegetable oils. In particular, the dispersion of vegetable oil sucrose ester resins was the focus of the work, with a water emulsifiable alkyd resin as a control. Sucrose ester resins of several fatty acids (soybean, safflower, linseed) were obtained from Procter and Gamble. We have also explored several routes to the synthesis of these resins. Waterborne coating systems are being designed from the ground up using scientific principles and systematic studies of the components of the coatings. Dispersions have been prepared using a high speed disperser by dispersing the resins into water in the presence of surfactants. The effects of surfactant type (composition) and amount on the rheological properties of the dispersions have been characterized. The aqueous dispersions are easily formed and are stable. The effect of thickeners on the rheology of the dispersions has been evaluated in order to design coatings having the appropriate rheological profile in order to insure good application properties as well as anti-sagging properties after the coating is applied. Pigmented coatings based on the aqueous dispersions have now also been prepared. Since the dispersed particles have low Tg, coalescence of the particles to form a good coating is excellent and coalescing aids (usually volatile organic compounds) are not required. A number of additional approaches to the synthesis of high performance coatings binder systems based on renewable resources are currently being pursued. In general, these approaches involve the addition of reactive functional groups to the multifunctional vegetable oil based resins. These are reactive functional groups typically used to form crosslinked high performance coatings. Due to the high degree of functionality of these resins, when reacted to form crosslinked coating films, we are obtaining thermoset materials which have a good combination of properties (e.g., hardness, adhesion, flexibility) and are superior in performance to similar functionalized vegetable oil systems. Three invention disclosures have been submitted to the NDSU Technology Transfer Office based on our research work. We expect that patent applications will be filed in early 2010. Several additional invention disclosures are in preparation. PARTICIPANTS: CoPI Dr. Dean C. Webster, Professor, has provided overall direction for the project. CoPI Dr. Stuart G. Croll, Professor, has provided overall direction for the project. Partha Sengupta, Postdoctoral Research Associate, has been involved in preparing the aqueous dispersions of the resins and evaluating rheological properties. Xiao Pan, Graduate Research Assistant, has conducted experiments to prepare sucrose esters of fatty acids. He has also introduced novel functional groups into the sucrose ester system. TJ Nelson, Graduate Research Assistant, is exploring the use of driers and the drying behavior of the sucrose esters of fatty acids. Umesh Harkal, Graduate Research Assistant, is synthesizing and characterizing fatty acid modified glycidyl carbamate resins. Adlina Paramarta, Undergraduate Research Student, is assisting with coating formulation, synthesis of novel functionalized multifunctional resins. TARGET AUDIENCES: The paint and coatings industry, including suppliers. Biomaterial supply (farming and crop processing) industry. PROJECT MODIFICATIONS: A one-year no-cost extension was requested and granted.
Impacts
While biobased materials have been used in paints and coatings for centuries, these technologies have not kept up with the performance demands of today's coatings, nor have they been able to keep up with current environmental regulations regarding the evolution of volatile organic compounds (VOCs). This project is designed to address these issues by designing coating polymers based substantially on renewable resources, such as sugars and oils, which have very low levels of VOCs, and can be used in high performance coatings. By designing new high performance coating systems based on renewable resources, these coating systems can be used to replace those based on petroleum derived chemistries, meet current demanding performance expectations, and also meet current environmental regulations. Our overall strategy has been to synthesize vegetable oil based compounds which have a high degree of fatty acid functionality, but a compact molecular structure. The compact molecular structure yields low viscosity and, as we have discovered, an easy-to-emulsify resin system. The high degree of functionality leads to high crosslink density in the autoxidatively cured coatings systems, resulting in high quality coatings. The findings related to the water emulsifiable systems are being prepared for publication. Several papers will also be presented at scientific conferences in the Spring of 2010. We are also conducting experiments to provide additional chemical functional groups to the vegetable oil based resins. The functional groups we have introduced are commonly used in the formation of high quality thermoset or crosslinked coatings via several different mechanisms (depending on the functional group). Preliminary results are highly promising in that coatings having a good combination of fast cure speed, good hardness, and good adhesion are produced. These results have led to the submission of several invention disclosures to the Technology Transfer Office at NDSU. Our ongoing studies have increased our knowledge in the structure-property relationships of these systems and shown that our compounds offer superior properties to that of the vegetable oil based resin systems explored to date. Several papers based on this chemistry will be presented at scientific conferences in the Spring of 2010. The systems we are exploring have a number of environmental benefits. First, our compounds have very little content from petroleum-based sources; they are substantially made from bio-derived, renewable chemicals. Second, many of the systems we are exploring have very little organic solvent content and thus do not contribute to air pollution. Thus, we have a "green+green" approach to new materials for the coatings industry.
Publications
- No publications reported this period
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