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Synthesis and Structural Characterization of Novel Epoxy Materials From Sucrose and Cotton

Synthesis and Structural Characterization of Novel Epoxy Materials From Sucrose and Cotton. Navzer D. Sachinvala,* 1 Alexander A. Lambert III, 1 Nicolette Prevost, 1 Karol Maskos, 2 and Walter P. Niemczura 3 1 Cotton Chemistry and Utilization Research Unit,

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Synthesis and Structural Characterization of Novel Epoxy Materials From Sucrose and Cotton

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  1. Synthesis and Structural Characterization of Novel Epoxy Materials From Sucrose and Cotton Navzer D. Sachinvala,*1 Alexander A. Lambert III,1 Nicolette Prevost,1 Karol Maskos,2 and Walter P. Niemczura3 1Cotton Chemistry and Utilization Research Unit, Southern Regional Research Center, USDA-ARS, New Orleans, LA; 2Coordinated Instrument Facility, Tulane University, New Orleans, LA; 3Department of Chemistry,University of Hawaii at Manoa, Honolulu, HI

  2. This Talk is Dedicated to Professors Shelby F. Thames & Morton H. Litt For teaching me how to chemo-rationally transform agriculturally derived starting materials into industrial polymeric products

  3. Why Develop New ProductsFrom Cotton & Sugar? • Emerge with better products • Diversify the markets in which these commodities do business • Stimulate economic opportunities in Rural America • Effect a return on investment

  4. Consider Some Sugar Data • Production (US, M-STRV) 1995 and 2000: 7.390 and 8.903 • Raw sugar value (per lb. US $) 1995 and 2000 $0.290 and 0.190, current <$0.17 • 2003 average production cost estimate per lb. For raw sugar in Louisiana: ~ $0.155 • Number of sugar mills in Louisiana: 1900 ~400; 1950 ~50; 2004 ~16

  5. Consider Some Cotton Data • US Market share for all cellulose fibers: 1970 = 43% of total fibers consumed; 2000 = 8% (Chem. & Eng. News, 5-15-00, p.25) • Formulators avoid using cotton in composites citing incompatibility with metals and plastics (Polymer Mater. Enc., 1996, Vol. C, Wiley, 1079)

  6. Why Epoxies? • Annual Use in US > 0.6 B.lb. • Cost of Epoxies range from: $2.10 to 40.00 per lb., depending on use • Compound annual rate of growth in epoxies ~ 2 to 6 %, depending on use • Current suppliers: Shell, GE, Lord, 3M, HB-Fuller, Ciba, Am.Cyanamid, Dexter, and Hardman, Inc.

  7. Building Materials Markets • 1997 Total Value of Shipments = $17.8 billion • Value added = $7.3 billion • Rate of growth (1992 to 2003) ~3 % per annum • Value of imports = $12.2 billion • Value of exports = $ 3.6 billion

  8. Sucrose and Cellulose Sucrose is a dimer comprising glucose and fructose Cellulose (cotton) is a b-D-anhydroglucose polymer sucrose cellulose

  9. New Products From Sucrose 42 pieces of intellectual property

  10. Thermal Stabilization Agents from Sucrose

  11. Thermal Studies by DSC & TGA

  12. % Remaining Wt. At 200C V/S Time Degradation studies were done in air. 4 Sample average / plotted value.

  13. Proposed Mechanisms for Thermal Stabilization of PMMAs Thermal stability of PMMAs at 200 C in air was seen with fully substituted carbohydrate-based ethers only, & not with esters

  14. Sucrose-Based Epoxies

  15. Reactions of Epoxies With Diethylenetriamine (DETA) Curing and Thermoset Properties DETA = diethylene triamine; H theoretical 119.19kJ/mol epoxy

  16. Dynamic Mechanical Analysis 3Pt Bending: DMA-7e Perkin Elmer; rectangular strips l x w x thickness = 20 x 7 x 1.5 mm; -150 to +200C; heating rate = 5 C/min; displacement amplitude 10m;  = 3Hz; Static F= 110% (110mN; Dynamic F = 100mN)

  17. Dynamic Mechanical Analysis Continued • KEY: • = EAS • = EMS • = ECS • = DGEBA

  18. Adhesion Tests Aluminum ASTM-D1002

  19. Reactions of Epoxies With PhenylalanineCuring and Thermoset Properties -PAA is Phenylalanine, TrOA is Trioctylamine

  20. Reactions of Epoxies With AnhydridesCuring and Thermoset Properties -MNDA is Methyl-5-Norborene-2,3-Dicarboxylate, TrOA is Trioctylamine

  21. EAS 3.2 Quantitative 13C NMR • Proton decoupler started just before the Rf pulse for carbon • Furthermore, the decoupler) is on during acquisition, but is off during relaxation and between pulses • Proton nOe is filtered in acquisition & further by processing the early part of the 13C FID • Then, the carbon signals are integrated (b’) (a, a) (c’) (c) (b) (b’)

  22. ECS-7.3 Quantitative 13C NMR (d’) # epoxy groups / sucrose = [(epoxy integrals) / (olefin + epoxy integrals)] x 8 (d) (b’ cis) (b’) trans (b) (c)

  23. 200 100 150 100 50 200 150 50 ppm ppm EMS-5.6 Quantitative 13C NMR Methallyl sucroses Epoxy methallyl sucroses

  24. New Chemistry With Cellulose • Cellulose • b-1-4 linked poly(anhydroglucose) with P2 symmetry • 3 OH groups have different reactivities • Not used as an asymmetric starting polymer for chirons • bears protection at the 1,4-ends • What are the rules for asymmetric reactions with cellulose?

  25. Cellulose Epoxides & Addition? “manno” “allo” • Selective synthesis methods? • Where will the nucleophile add? • Effect of the remote hydroxyl group when protected or unprotected?

  26. Complete Characterization of Cellulose Derivatives • Polymers for Advanced Technologies, 1999, 10, 311-320 • J. Poly. Sci.: Part A: Poly. Chem. Ed., 1999, 37, 4019-4032 • J. of Poly. Sci.: Part A: Poly. Chem. Ed., 2000, 38, 1889-1902 • Polymers for Advanced Technologies, 2002, 13, 413-427 • Polymers for Advanced Technologies.2002, 13, 66-79 • ACS Symposium Series 834, NMR Spectroscopy of Polymers in Solution and in the Solid State. American Chemical Society, Washington DC, 2003, 306-323 Work not published

  27. Proton NMR of Allyl Cellulose

  28. Carbon-13 NMR of Allyl Cellulose

  29. 1H-1H COSY Spectrum of Allyl Cellulose

  30. Total Correlation (TOCSY) Spectrum of the Anhydroglucose Portion of Allyl Cellulose

  31. 1H-1H COSY Spectrum of of the Allyl Appendages of the Polymer

  32. Heteronuclear Single Quantum Coherence (HSQC) Spectrum of Allyl Cellulose Spectrum shows one-bond correlations

  33. Allyl Cellulose - Repeating Unit Descriptors

  34. Heteronuclear Multiple Bond Correlation (HMBC) Spectrum of Allyl Cellulose Spectrum connects 1H and 13C nuclei 2 and 3 bonds away

  35. Total Correlation Spectroscopy TOCSY Spectrum of the Olefin Portion of Allyl Cellulose

  36. Heteronuclear Multiple Bond Correlation (HMBC) Spectrum of the Olefin Portion of Allyl Cellulose

  37. Crotyl to Epoxy Crotyl Celluloses Unlike allyl celluloses, epoxidation of crotyl celluloses is controlled: • 11, 33, 66, and 75% epoxidation obtained • Reactivity = 6 > 3 > 2 Crotyl celluloses Epoxy crotyl celluloses

  38. ECC 11% Epoxidation

  39. ECC 33% Epoxidation

  40. ECC 66% Epoxidation

  41. ECC 75% Epoxidation

  42. 2D-HSQC and Partial Line List (-ppm, CDCl3) 6 6a 2a 3a

  43. 2D-HSQC ECC-33% 3c(e) 6c(e) 6b(e) 6a(e)

  44. Complete Chemical Shift Assignments of Crotyl and Epoxy Crotyl Celluloses

  45. Acknowledgements • Funding through USDA ARS • Cooperative Agreement # 58-91H2-0-319 • CRIS # 6435-41000-064-00D • CRIS # 6435-41000-081-00D

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