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pinpicker produces light cellulose fluff. It consists of a rotating drum with sharp
pins protruding on the inner surface at close intervals. As the sheets of cellulose
are fed, they are being shredded continuously.
The pretreatment step, also known as swelling, is important to break the
hydrogen bond among the anhydroglucose units of cellulose subsequently
ensuring the hydroxyl group in cellulose is accessible for acetylation. Swelling
can be of vapor phase or slurry. In the vapor phase, a small amount of acetic acid
is added based on the weight of cellulose in a closed stainless steel vessel with
ambient temperature between 25 to 50C. They are left for 1 hour in the vessel
with minimum agitation. The uniform swelling of the cellulose occurs by both
condensation and vaporisation action of the acetic acid within the interstices of
fibres. If the cellulose contains 7% moisture and 35% glaical acetic acid, and
82/18 acetic acid and water is the best composition for swelling.
The slurry pretreatment involves a high liquid to cellulose ratio. The
cellulose is emerged in water or aqueous acetic acid and is vigorously agitated to
ensure uniform dispersion. The water is then exchanged with acetic acid through
a series of centrifuging or pressing the slurry. From time to time, the percentage
of acetic acid increases which in the end, results a dispersion with substantial
amount of acetic acid and only a small amount of water is present. It is important
for the water content to be low due to the high exothermic reaction at the
beginning of acetylation with acetic anhydride. The advantage of the slurry
pretreatment is that the wood pulp is not required to be shredded due to the
uniform dispersion. Normally, there is an activation step that follows. This
requires the addition of a catalyst, commonly sulfuric acid, to form an
intermediate which results in a faster acetylation.
The next stage, acetylation, occurs in a stainless steel acetylator equipped
with a cooling jacket and an agitator. The pretreated cellulose, acetic acid, acetic
anhydride and sulfuric are added into it. The acetic anhydride is added in excess
of 5%-15% weight to ensure complete reaction. The cooling jacket plays a vital
role during acetylation to control the temperature profile due to the high
exothermic reaction between acetic anhydride and water. Otherwise, significant
degradation will occur to the cellulose/cellulose acetate (Steinmeier, 2004). In
the case where high amount of catalyst is used, initial chilling of the reaction
mixture to the point of freezing crystals of acetic acid is necessary for heat sink.
The agitator is essential for a uniform dispersion of the reaction mixture during
acetylation. Acetylation initially occurs in the amorphous region of the cellulose.
The mechanism for acetylation may be described in two possible ways.
Nevertheless, both pathways utilizes the sulfuric acid to form as an intermediate.
The first chemical equation demonstrates the acetylation in terms of proton
activity:
R ( OH )n +n H 2 SO 4 + Ac 2 O R ( OS O2 OH ) +2 AcOH
OS O2 O
H +
R ( OSO2 OH ) + Ac 2 O R
H +
Ac 2 O
Alternatively, the cellulose acetic combines with sulfuric acid to form cellulose
sulfate:
R ( OH )n +n H 2 SO 4 + Ac 2 O R ( OS O2 OH ) +2 AcOH
R ( OSO2 OH ) + Ac 2 O R ( OS O2 OAc ) + AcOH
R ( OSO2 OAc ) + R ( OH ) n R ( OH )n1 OAc + R ( OS O 2 OH )
As acetylation proceeds, the viscosity of the reaction mixture increases and will
then form a uniform opaque viscous mixture. Later on, a clear mixture is
produced and the final product will have a viscous and clear characteristics. It is
crucial to take note that at the early stage, the acid dope appears to be grainy
and further acetylation needs to go beyond this grainy point until it appears to
be clear. This ensures the highly crystalline structure in the cellulose is
penetrated well by the reactants and acetylated. The acid dope will also attain
good filtration properties. Acetylation is stopped by the addition of water or
dilute acetic acid. This helps to destroy excess acetic anhydride and desulfate
residual sulfate linkages. Also, the water added into the reaction mixture ensures
that the latter is no more anhydrous because degradation of the produced
cellulose triacetate will occur much slower in an aqueous acetic system. The
stopping point helps to adjust the degree of polymerization which controls the
viscosity of the cellulose triacetate.