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Periodation and Sulfonation of FibersEnhanced Water Absorption
New Cellulosics
Nan Jiang, Jianguo Zhang, Zhen Dang, and Dr. Arthur J. Ragauskas
Presented by:Dr. Nan Jiang
Institute of Paper Science and TechnologyGeorgia Institute of Technology
Atlanta, GA 30332
Outline
Background and Motivation Periodation and Sulfonation of Fibers Enhanced Water Absorption New Cellulosics Future Work
Background and Motivation
New cellulosic material applicationsEnhanced water absorbing properties of fibers1) Grafting charge groups to fibers2) Oxidative formation of acid groupsi) TEMPO-mediated oxidations of fibers
ii) Periodation of FibersEnhance Water Absorbency of Fibers
Develop New Water Soluble Cellulose
Periodation and Sulfonation of Fibers Periodation of cellulosics
Sulfonation of Cellulosics
OO
HOOH
OH
SO3Na SO3Na n
SulfonationOO
O O
OH
NaHSO3
n
Manufacture of sulfonated cellulose with improved absorbent properties. Shet,R T,Wallajapet, P R R. PCT Int. Appl. 1997, 34 pp. 9721733.
OOHO
OH
OH
Periodation
NaIO4
OO
O O
OH
n nDAC
Functionalization of cellulose by periodate oxidation. Kim U, Kuga S. Cellulose Communications 2002, 9, 69-75
+ NaIO3 + H2O
Periodation and Sulfonation of Fibers Preparation of Cellulose Nanospheres and Whiskers
Facile synthesis of spherical cellulose nanoparticles Zhang, J., Elder, T. J., Pu, Y., Ragauskas, A. J. Carbohydrate Polymer 2007, 69, 607-611.The shape dependence of core-shell and hollow titania nanoparticles on coating thickness during layer-by-layer and sol-gel synthesis. Nelson K., Deng Y. Nanotechnology 2006, 17, 3219-3225.
ECF HW kraft pulp C0 (30.0g)
Cellulose nanospheres I C1 (~ 360 nm)
Cellulose nanospheres II C2 (~ 80 nm)
Cellulose whiskersC3 (L = ~ 300 nm W = 8 nm)
Periodation and Sulfonation of Fibers Periodation and Sulfonation of Cellulosics
OO
HOOH
OH
Periodation Sulfonation
NaIO4
OO
O O
OH
OO
HOOH
OH
SO3-
SO3-
NaHSO3
CX = ECF HW cellulose, nanospheres I, nanospheres II, and whiskers, X = 0, 1, 2, and 3LO: low oxidation using 0.3 g NaIO4 (1.40 mmol)HO: high oxidation using 0.6 g NaIO4 (2.80 mmol)LOS: low sulfonation on LO using 0.5 g of NaHSO3 (4.80 mmol)HOS: high sulfonation on HO using 1.0 g of NaHSO3(9.60 mmol)
CXLO, CXHO
CXLOS, CXHOS
n n
n
CX (2.5 g)
Periodation and Sulfonation of Cellulose
TEM images of, cellulose nanospheres (80 nm C2), oxidized nanospheres (C2LO), and sulfonated nanospheres (C2LOS)
100 nm100 nm
100 nm
Periodation and Sulfonation of Fibers
AFM images of a series of cellulosic materials
C0 C0LO C0LOS
C1 C1LO C1LOS
C3 C3LO C3LOS
Enhanced Water Absorption
Copper Number and Carbonyl group contentSamples Cu# Carbonyl group
(mmol/100 g fiber)
ECF HW cellulose (C0) 0.68 1.02
ECF HW cellulose LO (C0LO) 5.11 8.40
ECF HW cellulose HO (C0HO) 7.13 11.77
Cellulose nanospheres I (C1) 5.07 8.33
Cellulose nanospheres I LO (C1LO) 9.18 15.18
Cellulose nanospheres I HO (C1HO 13.14 21.78
Copper Number and Carbonyl group content
Enhanced Water Absorption
Samples Cu# Carbonyl group (mmol/100 g o.d. pulp)
Cellulose nanospheres II (C2) 5.38 8.85
Cellulose nanospheres II LO (C2LO) 9.96 16.48
Cellulose nanospheres II HO (C2HO) 14.86 24.65
Cellulose whiskers (C3) 3.56 5.82
Cellulose whiskers LO (C3LO) 7.62 12.58
Cellulose whiskers HO (C3HO) 10.45 17.30
Enhanced Water Absorption
Total acid groups measurements
0
1
2
3
4
5
6
7C0
C0LO
C0LOS
C0HO
C0HOS
C1
C1LO
C1LOS
C1HO
C1HOS
C2
C2LO
C2LOS
C2HO
C2HOS
C3
C3LO
C3LOS
C3HO
C3HOS
Total Acid Content (mmol/100g
fibers)
Enhanced Water Absorption
Water retention values (WRV)
Oxidation and Sulfonation of Cellulosics. Zhang, J., Jiang, N., Dang, Z., Elder, T. J.,and Ragauskas, A. J. Cellulose 2008, ASAP
0
0.2
0.4
0.6
0.8
1
1.2
1.4
C0C0
LOC0
LOS
C0HO
C0HO
S C1C1
LOC1
LOS
C1HO
C1HO
S C2C2
LOC2
LOS
C2HO
C2HO
S C3C3
LOC3
LOS
C3HO
C3HO
S
WRV
Enhanced Water Absorption
Conclusions
Periodation/Sulfonation of fibers can dramatically enhance water absorption properties by 8.0 –199.0%.
First time WRV have been shown to have a size dependence.
Application studies ongoing.
New Cellulosics
Water soluble property of periodation-sulfonation treated cellulose
OO
HOOH
OH
OO
O O
OH
OO
HOOH
OH
NaO3S SO3Na
n n
n
5.0 g cellulose oxidized by 10, 30, 50, 80, 100 wt% NaIO4
NaIO4
RT, 72h
OO
O O
OH
n
NaHSO3
RT, 12h
periodate oxidized cellulose treated by NaHSO3
New CellulosicsEffect of NaIO4 dosage (wt % of dry fibers) on the
water solubility of NaHSO3-treated fibers
From left to right, sulfonated cellulosics from 10, 30, 50, 80, 100 wt% NaIO4-treated fibers
13CPMAS of Cellulose
13C NMR of (100 wt%) NaIO4-oxidized fibers (D2O as solvent)
13C NMR of sulfonated fibers (100 wt% NaIO4-oxidized fibers treated with NaHSO3 in D2O)
New Cellulosics
New Cellulosics 1H NMR of sulfonated fibers (100 wt% NaIO4-oxidized dry fibers 100 mg
treated with 200 mg NaHSO3 in 1.0 g D2O)
1H NMR of sulfonated fibers (100 wt% NaIO4-oxidized dry fibers 100 mg treated with 200 mg NaHSO3 in 1.50 g D2O with 1.0 wt% DMSO as the internal standard)
New Cellulosics
Effect of NaIO4 dosage on the water solubility of sulfonated cellulose determined by 1H NMR analysis
0
10
20
30
40
50
60
0% 20% 40% 60% 80% 100%
NaIO4 dosage, wt % dry fibers
Wat
er s
olub
ility
of s
ulfo
nate
d fib
ers,
mg/
g
New Cellulosics
Conclusions
NaIO4 dosage have a significant effect on the water solubility of sulfonated fibers.
First time sulfonated fibers have shown excellent water solubility (as high as 5.0 g per 100 mL water at room temperature).
Application studies ongoing.
