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11.3.2.7 Degradation of Dissolving Pulps

The behaviour of dissolving pulps within heterogeneous degradation reactions

provides insight into their supramolecular structures, functionalities, and changes

In mwd. A comprehensive description of all relevant cellulose degradation processes

Is reviewed in Ref. [4]. The different modes of cellulose degradation comprise

chemical, mechanical, thermal, and radiation degradation. In many conversion

processes of cellulose, the molecular weight must be adjusted by controlled

degradation procedures.

The degradation of cellulose plays an important role in the chemical processing

of dissolving pulps. The aim of controlled cellulose degradation is to adjust polymer

properties related to the molecular weight such as solution viscosity (ethers)

or strength properties of the final product (regenerated fibers). The most important

conversion processes of dissolving pulps, viscose and cellulose ethers, operate

1056

11.3 Dissolving Grade Pulp

under alkaline conditions. There, molar mass is adjusted by oxidative alkaline degradation,

also known as ageing of alkali cellulose. In recent years, a new route of

controlled degradation of the dissolving pulp prior alkalization by high-energy radiation

has been extensively investigated and technologically developed by Fischer

et al. [88].

Alkali cellulose with a typical composition of 34% cellulose and 16% NaOH

(~1.9 mol NaOH mol–1 cellulose) is rather rapidly degraded at only a slightly elevated

temperature (30–50 °C), initiated by the uptake of oxygen. The reaction rate

can be accelerated by the addition of transition metal ions, particularly Co or Mn

salts. The course of the chain scissions, calculated from the weighted molecular

weight (determined by GPC measurement [68]) of alkali celluloses prepared from

both hardwood sulfite and PHK dissolving pulps as a function of reaction time at

50 °C, is illustrated graphically in Fig. 11.29.

0 2 4 6 8

0

5

10

15

20

HW-Sulfite HW-PHK

Chain Scissions [104/DP

w,t

-104/DP

w,0

]

Ageing time at 50 °C [h]

Fig. 11.29 Course of chains scissions (based on weighted

molecular weight) of alkali celluloses prepared from hardwood

sulfite and PHK dissolving pulps as a function of time

at 50 °C.

The ageing of alkali cellulose follows a pseudo zero-order reaction kinetics

based on the number-average degree of polymerization DPn, according to the following

expression [56]:

104

DPn_t _

104

DPn_0 _ _ kA t _1_

where kA is the reaction rate of the ageing process.

1057

11 Pulp Properties and Applications

The deviation from linearity, which is particularly discernible for alkali cellulose

made from a hardwood sulfite pulp, can be attributed to the change (decrease) in

polydispersity during degradation. Based on today’s knowledge of the reaction

mechanism, chain scission is initiated by the reducing endgroups. In agreement

with these considerations, oxidative alkaline degradation of sulfite pulp proceeds

faster as compared to the more narrowly distributed PHK dissolving pulp (see

Fig. 11.29).

The arguments in favor of electron beam treatment of dissolving pulp are a better

control of viscosity degradation following a strict random scission mechanism,

which results in better reactivity towards derivatization due to a better accessibility