synthesis and structural characterization of novel

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. 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

This Talk is Dedicated to Professors Shelby F. Thames & Morton H. Litt: 

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

Why Develop New ProductsFrom Cotton & Sugar?: 

Why Develop New Products From 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

Consider Some Sugar Data: 

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

Consider Some Cotton Data: 

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)

Why Epoxies?: 

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.

Building Materials Markets: 

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

Sucrose and Cellulose: 

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

New Products From Sucrose: 

New Products From Sucrose 42 pieces of intellectual property

Thermal Stabilization Agents from Sucrose: 

Thermal Stabilization Agents from Sucrose

Thermal Studies by DSC & TGA: 

Thermal Studies by DSC & TGA

% Remaining Wt. At 200C V/S Time: 

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

Proposed Mechanisms for Thermal Stabilization of PMMAs : 

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

Sucrose-Based Epoxies: 

Sucrose-Based Epoxies

Reactions of Epoxies With Diethylenetriamine (DETA) Curing and Thermoset Properties: 

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

Dynamic Mechanical Analysis: 

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)

Dynamic Mechanical Analysis Continued: 

Dynamic Mechanical Analysis Continued KEY: = EAS = EMS = ECS = DGEBA

Adhesion Tests Aluminum ASTM-D1002: 

Adhesion Tests Aluminum ASTM-D1002

Reactions of Epoxies With PhenylalanineCuring and Thermoset Properties: 

Reactions of Epoxies With Phenylalanine Curing and Thermoset Properties -PAA is Phenylalanine, TrOA is Trioctylamine

Reactions of Epoxies With AnhydridesCuring and Thermoset Properties: 

Reactions of Epoxies With Anhydrides Curing and Thermoset Properties -MNDA is Methyl-5-Norborene-2,3-Dicarboxylate, TrOA is Trioctylamine

EAS 3.2 Quantitative 13C NMR: 

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 (c) (b) (a, a) (b’) (b’) (c’)

ECS-7.3 Quantitative 13C NMR: 

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

EMS-5.6 Quantitative 13C NMR: 

EMS-5.6 Quantitative 13C NMR Methallyl sucroses Epoxy methallyl sucroses

New Chemistry With Cellulose: 

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?

Cellulose Epoxides & Addition?: 

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

Complete Characterization of Cellulose Derivatives: 

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

Proton NMR of Allyl Cellulose: 

Proton NMR of Allyl Cellulose

Carbon-13 NMR of Allyl Cellulose: 

Carbon-13 NMR of Allyl Cellulose

1H-1H COSY Spectrum of Allyl Cellulose: 

1H-1H COSY Spectrum of Allyl Cellulose

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

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

1H-1H COSY Spectrum of of the Allyl Appendages of the Polymer: 

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

Heteronuclear Single Quantum Coherence (HSQC) Spectrum of Allyl Cellulose: 

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

Allyl Cellulose - Repeating Unit Descriptors: 

Allyl Cellulose - Repeating Unit Descriptors

Heteronuclear Multiple Bond Correlation (HMBC) Spectrum of Allyl Cellulose: 

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

Total Correlation Spectroscopy: 

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

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

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

Crotyl to Epoxy Crotyl Celluloses: 

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

ECC 11% Epoxidation : 

ECC 11% Epoxidation

ECC 33% Epoxidation: 

ECC 33% Epoxidation

ECC 66% Epoxidation: 

ECC 66% Epoxidation

ECC 75% Epoxidation: 

ECC 75% Epoxidation

2D-HSQC and Partial Line List (-ppm, CDCl3): 

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

2D-HSQC ECC-33%: 

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

Complete Chemical Shift Assignments of Crotyl and Epoxy Crotyl Celluloses: 

Complete Chemical Shift Assignments of Crotyl and Epoxy Crotyl Celluloses

Acknowledgements: 

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