Final Report: Development of Green Chemistry for Syntheses of Polysaccharide-Based Materials

EPA Grant Number: R826123
Title: Development of Green Chemistry for Syntheses of Polysaccharide-Based Materials
Investigators: Wang, Peng George
Institution: Wayne State University
EPA Project Officer: Richards, April
Project Period: November 1, 1997 through October 31, 2000 (Extended to October 31, 2001)
Project Amount: $180,000
RFA: Technology for a Sustainable Environment (1997) RFA Text |  Recipients Lists
Research Category: Nanotechnology , Sustainability , Pollution Prevention/Sustainable Development


As we move into the 21st century, the world is facing an unprecedented challenge: environmental protection and sustainable economic growth. Because nonrenewable raw materials such as petroleum, natural gas, and coal for chemical and pharmaceutical industries are disappearing fast with increasing population pressure, development of environmentally friendly catalysis/biocatalysis processes and switch from the dependence on petroleum to renewable resources (mainly from agricultural feedstocks such as cellulose and starch) are strategic steps to face this challenge. This research program used renewable natural polysaccharides as a platform and lanthanide-based catalysts as a novel synthetic tool to develop environmentally friendly chemistry for synthesis of novel polysaccharide-based materials.

The major thrusts of this program were the development and application of lanthanide catalysis. Lanthanide triflates serve as stable Lewis acids under a nearly neutral condition to catalyze many organic transformations. Thus, some current industrial processes can be reengineered with this mild catalyst to reduce their negative environmental impacts. This program's two specific goals were to: (1) develop lanthanide triflates-promoted organic transformation and fully evaluate their industrial potentials in terms of solvent requirement, reactivity, and chemo-, regio-, and stereo-selectivity; and (2) apply the lanthanide triflates-promoted reaction onto natural polysaccharides, develop lanthanide-catalyzed synthesis of cellulose-ethers, and investigate lanthanide-catalyzed polymerization technology to graft polyesters onto polysaccharides.

Summary/Accomplishments (Outputs/Outcomes):

During the past 4 years, we have accomplished an enormous amount of work towards specific goal 1. We published 11 original research papers and developed many new types of organic reactions that can be catalyzed by lanthanides. These new reactions include: reactions of indoles with aldehydes or ketones; aqueous aza-Diels-Alder reactions; reactions of aldehydes and amines in aqueous solution; a variety of reactions catalyzed by lanthanide catalysts supported on ion exchange resins; aza-Diels-Alder reactions for sugar synthesis; reactions of imines with indole; polymeric La(H2Salen) complex; solid phase aza Diels-Alder reactions; reactions of imines with ethyl diazoacetate; electrophilic aromatic substitution with glyoxalate; and oxidative cleavage of benzylidene acetals using molecular oxygen. This fundamental research set up a solid base for industrial use of lanthanide catalysts to modify and change existing industrial processes to more environmental benign processes. Our accomplishments have been summarized in the four review articles we published. It should be mentioned that our review article in Chemtech (1999) was chosen by the American Chemical Society (ACS) as the best article in that issue, and has generated enormous response in both academics and industry. Since then, it has been highly cited?both nationally and internationally. We have been contacted by several industry companies, including Dow Chemicals, Hercules, Inc., and others for either consulting or for more information to implement our lanthanide-based reactions into industrial process.

Although we do not have enough time or funding to fully work on specific goal 2, we have made good progress. We published one paper on using lithium chloride as a catalyst for ring-opening polymerization of lactide. Detailed studies have been carried out to investigate lanthanide triflates-catalyzed ring-opening reactions of epoxides with alcohols, monosaccharides, and some polysaccharides. Different lanthanides and solvent systems have been tested for optimal reaction conditions. In addition, lanthanide triflates were examined as catalysts for the preparation of polysaccharide-polyester copolymers. It should be emphasized that we have been closely collaborating with Hercules, Inc., to implement these studies to industrial processes. Hercules, Inc., is the largest producer in the world of sugar-based water soluble polymers. Their main products include: hydroxyetheylcellulose (HEC) and hydroxypropylcellulose (HPC). So far, three joint patent disclosures have been written and filed with the patent office at Hercules, Inc. One patent application has been filed with the U.S. patent office. We have demonstrated that the ring-opening reaction of cyclohexene oxide proceeds smoothly and quantitatively at room temperature under the catalysis of lanthanum or ytterbium triflate (5 mol %). We have carried out preliminary studies on the corresponding reactions with some cellulosic derivatives such as HEC and HPC. The reactions were performed both homogeneously (in DMF) and heterogeneously (in THF). In both cases, the parent HEC and HPC were modified effectively and showed significant changes in physical properties. We showed that Ln(OTf)3 can be used as an effective catalyst for the ring-opening polymerization of lactide (bulk) in the presence of benzyl glucopyranoside. Using N, N-dimethylacetamide (DMAc) as the solvent, we successfully applied this technology to the synthesis of HEC-PLA and HPC-PLA copolymers. In summary, our collaboration with Hercules, Inc., will continue, and we will continue to transfer the lanthanide-catalyzed reactions for industrial uses.

Journal Articles on this Report : 12 Displayed | Download in RIS Format

Other project views: All 21 publications 14 publications in selected types All 12 journal articles
Type Citation Project Document Sources
Journal Article Chen YS, Wang PG. Facile oxidative cleavage of benzylidene acetals using molecular oxygen catalyzed by N-hydroxyphthalimide/Co(OAc)(2). Tetrahedron Letters 2001;42(30):4955-4958 R826123 (Final)
not available
Journal Article Yu LB, Li J, Ramirez J, Chen D, Wang PG. Synthesis of azasugars via lanthanide-promoted aza Diels-Alder reactions in aqueous solution. Journal of Organic Chemistry 1997;62(4):903-907 R826123 (Final)
not available
Journal Article Xie WH, Fang JW, Li J, Wang PG. Aziridine synthesis in protic media by using lanthanide triflates as catalysts. Tetrahedron 1999;55(45):12929-12938 R826123 (Final)
not available
Journal Article Xie W-H, Heeg MJ, Wang PG. Formation and crystal structure of a polymeric La(H2Salen) complex. Inorganic Chemistry 1999;38(10):2541-2543. R826123 (Final)
not available
Journal Article Xie W-H, Jin Y-F, Wang PG. Lanthanide triflates as unique catalysts: effecting organic transformations in aqueous media. Chemtech 1999;29(2):23-29. R826123 (Final)
not available
Journal Article Xie WH, Bloomfield KM, Jin YF, Dolney NY, Wang PG. Lanthanide triflates catalyzed reactions of imines with indole in protic media. Synlett 1999;(4):498-500 R826123 (Final)
not available
Journal Article Xie WH, Chen DP, Fan XH, Li J, Wang PG, Cheng HN, Nickol RG. Lithium chloride as catalyst for the ring-opening polymerization of lactide in the presence of hydroxyl-containing compounds. Journal of Polymer Science Part A-Polymer Chemistry 1999;37(17):3486-3491 R826123 (Final)
not available
Journal Article Yu LB, Chen DP, Li J, Ramirez J, Wang PG, Bott SG. Lanthanide-promoted reactions of aldehydes and amine hydrochlorides in aqueous solution. Synthesis of 2,3-dihydropyridinium and pyridinium derivatives. Journal of Organic Chemistry 1997;62(1):208-211 R826123 (Final)
not available
Journal Article Yu LB, Chen DP, Li J, Wang PG. Preparation, characterization, and synthetic uses of lanthanide(III) catalysts supported on ion exchange resins. Journal of Organic Chemistry 1997;62(11):3575-3581 R826123 (Final)
not available
Journal Article Zhang W, Xie W-H, Fang J-W, Li J, Chen X, Wang J-Q, Janczuk A, Wang PG. Recent progress in glycochemistry and green chemistry. Current Organic Chemistry 1999;3(3):241-267. R826123 (Final)
not available
Journal Article Zhang W, Xie W-H, Fang J-W, Wang PG. Ytterbium(III) trifluoromethanesulfonate catalyzed solid phase aza Diels-Alder reaction and subsequent facile adduct release. Tetrahedron Letters 1999;40(45):7929-7933. R826123 (Final)
not available
Journal Article Zhang W, Wang PG. Ytterbium(III) trifluoromethanesulfonate catalyzed electrophilic aromatic substitution with glyoxalate and lipase-mediated product resolution: a convenient route to optically active aromatic alpha-hydroxy esters. Journal of Organic Chemistry 2000;65(15):4732-4735. R826123 (Final)
not available

Supplemental Keywords:

benign process, environmentally friendly solvent, biodegradable materials, renewable resources, biomass., RFA, Scientific Discipline, INTERNATIONAL COOPERATION, Sustainable Industry/Business, POLLUTION PREVENTION, Sustainable Environment, Environmental Chemistry, cleaner production/pollution prevention, waste reduction, Technology for Sustainable Environment, Analytical Chemistry, Economics and Business, Chemicals Management, lanthanide catalysts, cleaner production, waste minimization, toxic use reduction, alternative materials, catalysts, hazardous waste, alkylation reaction, polysaccairde, polymer design, source reduction, environmentally-friendly chemical synthesis

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Progress and Final Reports:

Original Abstract
  • 1998
  • 1999
  • 2000