Ionic Crosslinking of Cotton: Peter J. Hauser, C. Brent Smith, and Mohamed M. Hashem

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AUTEX Research Journal, Vol.

4, No2, June 2004 © AUTEX

IONIC CROSSLINKING OF COTTON


1* 1 2
Peter J. Hauser , C. Brent Smith , and Mohamed M. Hashem
1
North Carolina State University, Raleigh, North Carolina, USA
2
National Research Center, Cairo, Egypt
*
Corresponding author’s address
Campus Box 8301, North Carolina State University
Raleigh, North Carolina 27695
Telephone: 919-513-1899 Fax: 919-515-6532
email: peter_hauser@ncsu.edu

Abstract
Cellulose crosslinking is a very important textile chemical process, and is
the basis for a vast array of durable press- and crease-resistant finished
textile products. N-methylol crosslinkers containing formaldehyde give fabrics desirable
properties of mechanical stability (e.g. crease resistance, anti-curl, shrinkage resistance,
durable press), but also impart strength loss and the potential to release formaldehyde, a
known human carcinogen. Other systems, e.g. polycarboxylic acids, have been tested
with varying degrees of success. We have developed methods of forming ionic
crosslinks that provide outstanding crease-angle recovery performance, as well as
complete strength retention in treated goods, without the potential for
releasing any low-molecular weight reactive materials, such as formaldehyde. Our work is
based on reactions of cellulose with materials that impart an
ionic character to the cellulose, e.g. chloroacetic acid for negative charges or
3-chloro-2-hydroxypropyl trimethyl ammonium chloride for positive charges. These
reactions produce ionic celluloses that can then sorb a polyionic material of opposite
charge to form crosslinks. Cellulose treated with cationized chitosan after
carboxymethylation showed significant increases in crease recovery angles without
strength loss.

Keywords
cellulose crosslinking, ionic crosslinking, durable press, wrinkle resistance

Introduction
The crosslinking of cellulose is a crucial textile chemical process, and provides the textile
manufacturer a multitude of commercially important textile products. The most commonly used
crosslinking systems are based on N-methylol chemistry. These crosslinkers give fabrics many
desirable mechanical stability properties (e.g. crease resistance, anti-curl, shrinkage resistance,
durable-press), but also impart strength loss and the potential to release formaldehyde, a known
human carcinogen. [4] Other chemical systems that do not contain formaldehyde, e.g. polycarboxylic
acids, have been explored with varying degrees of success.[9,10] In this work we report on methods of
forming ionic crosslinks, rather than the typical covalent crosslinks, to provide crease-angle recovery
performance without formaldehyde release.

Ionic cellulose can be produced with a variety of reagents. Figure 1 provides examples of obtaining
anionic cellulose by reacting chloroacetate with cellulose and cationic cellulose by a similar reaction
with 3-chloro-2-hydroxypropyl trimethyl ammonium. These reactions produce ionic celluloses that can
then sorb a polyelectrolyte of opposite charge to form crosslinks.

There are numerous strategies for producing ionic crosslinks. In this work, we will discuss the use of
cationized chitosan to crosslink cotton which has been made anionic with chloroacetate.

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The reaction of chitosan with 3-chloro-2-hydroxypropyl trimethyl ammonium leads to a cationized


polymer that maintains its cationic character regardless of pH (Figure 3).

ClCH2COO + Cellulose OH Cellulose O CH2COO


Preparation of anionic cellulose by reaction of cellulose with chloroacetate

ClCH2CHCH2N(CH3)3 + Cellulose OH Cellulose O CH2CHCH2N(CH3)3


OH OH

Preparation of cationic cellulose by reaction with 3-chloro-2-hydroxypropyl trimethyl ammonium ion

Figure 1. Preparation of ionic cellulose

Chitosan is obtained by alkaline hydrolysis of the naturally occurring polysaccharide chitin (Figure 2).

O
CH2OH NHCCH3 CH2OH NH2
O O OH O O
OH OH OH OH
O O O O O
O
NHCCH3 CH2OH NH2 CH2OH
O

chitin chitosan

Figure 2. Preparation of chitosan from chitin

CH2CHCH2N(CH3)3 CH2OH NHCH2CHCH2N(CH3)3


CH2OH NH2
Cl OH O O OH
O O OH OH
OH OH O O
O
O O O OH (CH3)3NCH2CHCH2NH CH2OH
NH2 CH2OH
OH
cationized chitosan
Figure 3. Preparation of cationized chitosan

Experimental
Anionic cellulose was produced with various carboxymethyl content (up to 125 mmol per 100 g fabric)
by a method similar to those previously reported [1, 2, 5, 6, 7, 8]. Bleached cellulosic fabric was
impregnated with 20% aqueous NaOH for 10 minutes at room temperature, followed by padding to a
o
wet pickup of 100%. Samples were dried at 60 C. These alkali-treated samples were then steeped for
5 minutes at room temperature in aqueous solutions of chloroacetic acid that had been neutralized
with sodium carbonate at various concentrations (0 to 3.0 M). These samples were then squeezed to
o
100% wet pickup, sealed in plastic bags and heated at 70 C for 1 hour. The samples were then
washed and dried at room temperature. Blanks were included. This produced 7 different levels of
carboxymethylation, i.e. 6.15, 30.2, 60.7, 87.1, 97.3, 114.5, and 123.7 mmols of carboxymethyl groups
per 100 grams of fabric, as determined by titration.

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Cationic chitosan was produced by the reaction of 85% N-deacetylated chitin with 3-chloro-2-
hydroxypropyl trimethyl ammonium chloride using a method that differed somewhat from the method
previously reported by Kim et al. [3]. 161 grams of 85% N-deacetylated chitin was slurried in 1156
grams of 69% w/w solution of 3-chloro-2-hydroxypropyl trimethyl ammonium chloride. NaOH (50%
w/w) was added dropwise to maintain pH of 10 to 11. The slurry was stirred overnight; then the
o
temperature was raised to 95 C for 4 hours, cooled to room temperature and adjusted to pH 7 with
acetic acid. The resulting reaction product was soluble in the reaction mixture. When recovered by
drying, the resulting product was easily re-dissolved in room-temperature water at pH 7.

To accomplish the ionic crosslinking, cationized chitosan was applied to the anionic cellulosic fabrics
o
by padding through solutions of cationized chitosan in water at 100% wet pickup, then drying at 105 C.
Various concentrations of cationic chitosan were used in the padding bath, i.e. 0, 0.5, 2, 4, and 6%
solution concentration.

Materials
The materials used are presented in Table I.

Table I. Materials

Material Supplier

Chloroacetic acid reagent grade, Fisher Scientific

3-chloro-2-hydroxypropyl trimethyl
CR2000 cationic reagent, 69% solution, Dow Chemical,
ammonium chloride

Chitosan 85% N-deacetylated chitin, Vanson Chemicals


2
Cotton fabric scoured and bleached plain weave, 114 g/m ,Testfabrics

All chemicals were used as received.

Methods of Analysis
Nitrogen analysis was provided by Dow Chemical Company using a Leuco HCN Analyzer.

Carboxymethyl content of cellulosic fabrics was determined as follows. Samples were steeped
overnight in 0.1% HCl solution at room temperature. These were then washed with distilled water until
o
the wash water showed no presence of chloride by an AgNO3 drop test. Samples were dried at 105 C,
then brought to standard conditions. Exactly 0.3 grams of each sample was carefully weighed and
combined with 100 mL distilled water and 20 mL of 0.05N NaOH in a beaker. This mixture was titrated
with standardized HCl solution to a phenolphthalein end point. The carboxymethyl content was
calculated as follows.

mmols carboxymethyl content per 100 grams = 100 * (Vo – V) * (NHCl) / (0.3)

where V is the titer for the sample, Vo is the titer for the blank, and NHCl is the normality of the HCl
titrant.

Crease angle measurements were made by AATCC Standard Test Method 66, Wrinkle Recovery of
Fabrics: Recovery Angle Method. The presented results are the sum of the recovery angle of the
tested fabric in the warp and weft directions. Breaking strength was determined with an Instron tensile
tester using ASTM test method D1682.

Results and Discussion


The nitrogen content of the treated fabrics are shown in Table II. As expected, the nitrogen content
increases as the application level of cationized chitosan increases. Laundering the treated fabrics did
not decrease the nitrogen content, indicating that a durable finish was obtained.

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Table II. Nitrogen Content for Treated Fabrics (% Nitrogen)


-
COO content, Cationized chitosan concentration in pad bath
mmoles/100g 0% blank 0.5% 2% 4% 6%
6.2 0% 0.015% 0.021% 0.072% 0.19%
30.2 0% 0.07% 0.21% 0.26% 0.31%
60.7 0% 0.16% 0.30% 0.38% 0.42%
87.1 0% 0.25% 0.31% 0.38% 0.47%
97.3 0% 0.33% 0.39% 0.48% 0.49%
114.5 0% 0.33% 0.39% 0.49% 0.51%
123.7 0% 0.36% 0.41% 0.49% 0.52%

The dry and wet wrinkle recovery angles measured for the treated fabrics are given in Table III and
Figures 4 and 5. As can be seen, both recovery angles increase as the carboxymethyl content and the
cationized chitosan application level increase. The wet recovery angles in particular show remarkable
increases.

Table III. Dry and wet wrinkle recovery angles for treated fabrics (dry/wet)
-
COO content, Cationized chitosan concentration in pad bath
mmoles/100g 0% blank 0.5% 2% 4% 6%
6.2 140/130 145/200 180/250 156/200 140/260
30.2 145/135 156/208 188/206 172/250 164/264
60.7 140/144 154/204 162/200 190/252 160/274
87.1 142/150 162/200 172/200 166/250 180/295
97.3 145/148 158/200 162/230 174/272 180/295
114.5 145/140 154/226 160/256 178/284 184/320
123.7 148/130 156/224 166/286 180/298 192/326

200

190
Dry WRA (degrees)

180

170

160

150

140
0 0.2 0.4 0.6
Nitrogen Content (%)

Figure 4. Effect of treatment on dry wrinkle recovery angle

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300
Wet WRA (degrees
250

200

150
0 0.2 0.4 0.6

Nitrogen Content (%)

Figure 5. Effect of treatment on wet wrinkle recovery angle

The breaking strengths of the treated fabrics are given in Table IV and Figure 6. Unlike other
crosslinking systems, this ionic system not only does not adversely effect the fabric breaking strength,
but also the strength actually increases as the treatment level is increased.

Table IV. Breaking strengths of treated fabrics (N)


-
COO content, Cationized chitosan concentration in pad bath
mmoles/100g 0% blank 0.5% 2% 4% 6%
6.2 143 145 147 156 156
30.2 143 148 151 159 166
60.7 147 136 115 144 166
87.1 141 149 155 164 168
97.3 136 137 148 154 169
114.5 134 138 148 155 170
123.7 123 130 153 158 174

180
Breaking Load (grams

170
, cN

160
150
140
130
120
0 0.2 0.4 0.6
Nitrogen Content (%)

Figure 6. Effect of treatment on strength

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Conclusions
Wrinkle resistance in cellulosic fabrics can be achieved with ionic crosslinks. Carboxymethylated
woven cotton fabric treated with cationized chitosan showed significant increases in wrinkle angle
recovery without strength loss. This process allows for enhanced wrinkle resistance without the
chance of formaldehyde release.

References
[1] Daul, G., et al, Studies on the Partial Carboxymethylation of Cotton, Textile Res. J., 22(12),
1952, p 787.
[2] Hashem, M. et al, Synthesis of Reactive Polymers and Their Applications to Cotton Fabrics as
Permanent Size, Molecular Crystals and Liquid Crystals Science and Technology Section A:
Molecular and Liquid Crystals, 353, 2000, p 109.
[3] Kim, Y. et al, Synthesis of a Quaternary Ammonium Derivative of Chitosan and Its Application to
a Cotton Antimicrobial Finish, Textile Res. J., 68(6), 1998, p 428.
[4] Peterson, Harro, Cross-Linking with Formaldehyde-Containing Reactants, Chapter 2 in
Functional Finishes, Volume II, Part B; Lewis, M.; Sello, S. B. Eds.; Dekker, New York, 1983; p
200.
[5] Racz, I. et al, Crystallinity and Accessibility of Fiberous Carboxymethyl Cellulose by Pad-Roll
Technology, J. Applied Poly. Sci., 62, 1996, p 2015.
[6] Racz, I. and Borsa, J., Carboxymethylated Cotton Fabric for Pesticide-Protective Work Clothing,
Textile Res. J., 68(1), 1998, p 69.
[7] Racz, I. et al, Fiberous Carboxymethyl Cellulose by PAd Roll Technology, Textile Res. J., 65(6),
1995, p 348.
[8] XiQuan, L. et al, Kinetics of the Carboxymethylation of Cellulose in the Isopropyl Alcohol
System, Acta Polymerica, 41(4), 1990, p 220.
[9] Yang, C. et al, Nonformaldehyde Durable Press Finishing of Cotton Fabrics by Combining Citric
Acid with Polymers of Maleic Acid, Textile Res. J., 68(5), 1998, p 457.
[10] Yang, C. and Wei, W., Evaluating Glutaraldehyde as a Nonformaldehyde Durable Press
Finishing Agent for Cotton Fabrics, Textile Res. J., 70(3), 2000, p 230.

Acknowledgment
The authors thank Dow Chemical Company for financial support and nitrogen analyses.

∇∆

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