144
of 500,000 to 1,000,000 g/mol, i.e. 3,000 to 5,000 glucose units per molecule. The molecules are
stretched and form crystalline micelles. This explains the outstanding strength of cellulose. How-
ever, polymers with crystalline micelles are insoluble in solvents and therefore make unsuitable
coating raw materials. The most important use of cellulose is in the preparation of textile fibres.
Modifications of cellulose (esters, ethers, nitrate) afford a means of using cellulose for paints. For
solvent-borne basecoats, the most important cellulose derivative is cellulose acetobutyrate.
Production of cellulose butyrate requires very pure cellulose. In the past, this was prepared from
cotton, but now is obtained from wood. The cellulose fibres are dispersed in acetic acid at 50
to 80 °C and then treated with a mixture of acetic anhydride and butyric anhydride, and some
sulphuric acid. Nearly all the hydroxyl groups are transformed into ester groups. The virtually
totally esterified cellulose is soluble in acetic acid. To an extent depending on the temperature and
duration, the large molecules of cellulose are cleaved into smaller molecules. Acidic cleavage of
glycoside bridges affords molecules containing only 100 to 350 glucose units. For optimum solu-
bility and compatibility, some of the ester groups are saponified by adding water to the reaction
mixture. Some free hydroxyl groups are generated thereby. This is accompanied by decomposition
of polymer molecules. Figure 3.7.5 shows the structure of a typical molecular segment of cellulose
acetobutyrate.
The available types of cellulose butyrate differ in molecular size (as measured and defined by
the viscosity of a test solution), the number of acetate and butyrate groups, and the number
of free hydroxyl groups. A typical cellulose acetobutyrate for metallic basecoats
[124]
consists
of 13.0 to 16.0 % by weight acetate groups, 33.0 to 38.0 % butyrate groups, and has an average
hydroxyl content of 1.8 % by weight. The dynamic viscosity is 790 to 1,900 mPa s (test solution
15 % by weight in butyl acetate). This type of cellulose acetobutyrate is soluble in esters, ketones,
glycol ethers, and glycol ether esters; it is thinnable with aromatic hydrocarbons or alcohols, or
both. Although there are free hydroxyl groups, their participation in crosslinking reactions is
implausible. While the crystallinity of cellulose is widely degraded by esterification, the aceto-
butyrate molecules – mainly the high-molecular types – still have a tendency to associate. This
tendency to form molecular associations is the reason that domains form in the film structure.
Provided that such domains do not influence the effect, they are advantageous as they boost the
resistance of basecoats to redissolving. The domains are visible under an interference micro-
scope. The higher the molecular mass of cellulose acetobutyrate, the better is its resistance to
redissolving, the better the resistance of basecoat films to chemicals, solvents and mechanical
Figure 3.7.5: Structure of a molecular segment of cellulose acetobutyrate
Automotive
OEM coatings
145
stress, the lower is the compatibil-
ity with other resins and the lower
is the solids content at application
viscosity of the basecoat thereof.
The influence of low-molecular cel-
lulose acetobutyrates on film prop-
erties is quite the opposite. High
quantities
of butyrate promote
solubility and compatibility, while
high quantities of acetate support
resistance to redissolving. High
quantities of hydroxyl groups pro-
mote compatibility with combina-
tion
resins
[125]
.
On account of the molecular struc-
ture
of cellulose acetobutyrate
and the residual tendency to form
molecular associations, the drying
properties of solutions of cellulose acetobutyrate are quite different from those of conventional
resins. Initially, the solvents evaporate much faster than other resins. However, at the end of
physical film formation, there is greater retention of residual solvents in the coiled molecular
structure of the cellulose acetobutyrate film. Such drying properties are advantageous for resist-
ance to redissolving and also promote levelling. The different evaporation properties of cellulose
acetobutyrate solutions and other resins are compared in Figure 3.7.6.
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