Quaternized xylans: synthesis and structural characterization

doi:10.1016/0144-8617(94)90075-2

Carbohydrate Polymers

Volume 24, Issue 4, 1994, Pages 301-308

https://doi.org/10.1016/0144-8617(94)90075-2 Get rights and content

Abstract

Quaternization xylans were prepared by treating xylans differing in structural and molecular properties with 3-chloro-2-hydroxypropyltrimethylammonium chloride (CHMAC) in aqueous NaOH under mild reaction conditions. The degree of substitution with quaternary ammonium groups can be monitored by altering the amount of CHMAC at optimum molar ratios of NaOH/CHMAC in the range 1·2-1·6, without changing the structure of the xylan backbones. Hot water pretreatment of the xylans in the alkaline activation step significantly enhances their reactivity. The presence of alkylammonium substituents was revealed by IR and NMR spectroscopy. The applicability of quaternized xylans as a retention aid in papermaking is demonstrated on thermomechanical pulp. Xylans, therefore, represent an important renewable resource for the production of novel cationic biopolymers.

References (31)

M. Antal et al.
Carbohydr. Polym.
(1992)
A. Deratani et al.
Carbohydr. Res.
(1989)
A. Domard et al.
Int. J. Biol. Macromol.
(1986)
A. Ebringerová et al.
Carbohydr. Polym.
(1992)
P.A.J. Gorin
Adv. Carbohydr. Chem. Biochem.
(1981)
S. Katsura et al.
Carbohydr. Polym.
(1992)
E. Loubaki et al.
Eur. Polym. J.
(1991)
R.A.A. Muzzarelli et al.
Carbohydr. Polym.
(1985)
P. Odonmažig et al.
Carbohydr. Res.
(1990)
B. Philipp et al.
Carbohydr. Res.
(1987)

M. Antal

M. Antal et al.

Cellul. Chem. Technol.

(1980)

M. Antal et al.

J. Appl. Polym. Sci.

(1984)

M. Antal et al.

Das Papier

(1991)

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Citation Excerpt :
The signals on the lower chemical shifts, from 58 to 76 ppm, correspond to the carbons that are more shielded and so are at lower shifts; that is, the other carbons from the Xy backbone (b, c, d, e) and glucuronic acid and methyl glucuronic acid substituents (Fundador et al., 2012; Liu et al., 2018b; Zhang et al., 2017). As observed in Fig. 5 for the QXy sample, when compared with the Xy spectra, the presence of extra signals at 17 and 54 ppm are noticed, in the form of sharp singlets, which correspond to the carbons of the methyl groups of quaternary ammonium, thus confirming the incorporation of CHPMAC in the xylan chain (Ebringerová et al., 1994). For the SXy sample, as seen in Fig. 5, an extra signal is observed at 32 ppm, in the form of a sharp singlet, in the most shielded region, which corresponds to the carbon e of the xylose chain, further away from the sulfate substituent groups on the second carbon (Šimkovic et al., 2011b).
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Quaternized xylans: synthesis and structural characterization

Abstract

Carbohydr. Polym.

Carbohydr. Res.

Int. J. Biol. Macromol.

Carbohydr. Polym.

Adv. Carbohydr. Chem. Biochem.

Carbohydr. Polym.

Eur. Polym. J.

Carbohydr. Polym.

Carbohydr. Res.

Carbohydr. Res.

Cellul. Chem. Technol.

J. Appl. Polym. Sci.

Das Papier