THE CELLULOSE DERIVATIVES

Cellulose Gum, Methylcellulose,

Methylhydroxypropylcellulose, and
Hydroxypropylcellulose

Chemistry, Functionality, and Applications

Andrew C. Hoefler
Brookside Consulting Ltd
321 Mill Pond Lane
Oxford, PA 19363
610-613-2698
ahoefler@aol.com
This presentation will cover the important food grade cellulose derivatives, starting with cellulose
gum or "CMC".

Figure 1 is a diagrammatic representation of a cellulose molecule. Note that each glucose unit in
the cellulose chain has three hydroxyl groups, each of which is capable of hydrogen bonding to an
adjacent molecule. In the bottom of Figure 1, we indicate cellulose more pictorially as a series of
circles connected together in a long, linear chain.

Figure 2 shows a group of cellulose molecules in water. Because of the abundance of hydroxyl
groups, and their ability to hydrogen bond to a neighboring molecule, the chains are bound tightly
together. Water molecules, at any temperature, cannot force their way in between the chains to
hydrate them, thus cellulose is water insoluble ( which is just as well, since most of our houses are
made of wood. I certainly would not want my house to dissolve the next time it rains! )

2
Figure 3 (previous page) illustrates the reaction for the manufacture of CMC. It is essentially a two
step process. In the first step, cellulose is suspended in alkali to open the bound cellulose chains,
allowing water to enter. Once this happens, the cellulose is then reacted with sodium
monochloroacetate to yield sodium carboxymethyl cellulose.

An idealized unit structure of CMC is depicted in figure 4. The CMC shown here has a D.S.
(Degree of Substitution) of 1.0. If the remaining two hydroxyl groups on this unit became
substituted, the D.S. would be 3.0. A D.S. of 3.0 is the theoretical maximum one could attain.

Figure 5 is a pictorial representation of CMC molecules. Note that the carboxymethyl groups
protrude from the cellulose backbone, such that the hydroxyl groups of the backbone cannot get
close enough to hydrogen bond to each other. The result is that even in the dried state, water can
slip in between the CMC molecules and hydrate them, causing them to "peel apart" from each
other and go into solution. As a result, cellulose gum is water soluble while cellulose is not.

3
Figure 6 depicts the nomenclature for Hercules cellulose gum. The specific product described is
cellulose gum type 7H3SXF. The "7" stands for the degree of substitution. In the food industry,
there are "7" and "9" types of substitution. The pharmaceutical industry also has a "1.2" type to
work with. The "H" signifies a high viscosity grade, and the "3" is a reference point which defines
the maximum viscosity of the gum in a 1% solution at 25C (in this case, 3000 centipoise). There
are "L", "M", and "H" types, representing low, medium, and high viscosity respectively. The "S"
stands for special rheological properties (smooth flow). There are "S" types for smooth flow, and
"O" types for tolerance in acidic systems. Both of these types show considerably less thixotropy
than the randomly substituted regular types of cellulose gum (more will be said about this later).
The "X" stands for fine grind material, while a "C" would indicate a coarse particle size, and no
letter would indicate a "regular" particle size. The "F" represents food grade (FCC), while a "P"
would be pharmaceutical grade (USP).

Some typical viscosity values are shown in Figure 7. Please note that "L" and "M" types are
measured at a 2% concentration, while "H" types are measured at 1%. Figure 8 shows the
concentration versus viscosity relationship in a more visual fashion.

4
The effect of the Degree of Substitution on the properties of CMC is shown in figure 9. Tolerance
to salt increases and tendency towards thixotropic behavior decreases as the degree of
substitution increases. The slight change in density and hydroscopicity are of no importance to a
food technologist.

There is another factor which is as important as the Degree of Substitution, and that is the
"Uniformity of Substitution", which is shown visually in Figure 10. The "smooth" or non-substituted
regions of a non-uniformly substituted molecule behave just like cellulose because they are still
cellulose! These regions can hydrogen bond to a similar region on an adjacent molecule, leading
to the buildup of a loose gel network (Figure 11).

5
This buildup is time dependent, and is called "thixotropy". The loose gel network can be disrupted
by shearing the CMC solution, but upon standing under no shear conditions the network will
reform over time.

Visually, the difference between uniformly and non-uniformly substituted CMC solutions can be
seen in Figure 12. Smooth flowing CMC types are desirable for food systems such as syrups or
frostings where smooth consistency is a must. Thixotropic CMC would find use in structured,
grainy foods such as sauces or purees.

6
Cellulose gum is probably the fastest gum to hydrate in cold water. Consequently, it is the gum
most like to form lumps when dispersed into water, due to it's rapid swelling in water. To
overcome the problem described above, four procedures are recommended in Figure 13:

Method 1: direct addition:

Here the gum is added directly to the vortex of a vigorously agitated body of water. The rate of
addition should be slow enough to keep the particles separated, but fast enough so that all of the
gum is added before the vortex disappears. The reason for this is that it is extremely difficult to
thicken an already viscous solution of cellulose gum by adding more dry powder. The direct
addition method is usually encountered in highly controlled processing situations.

Method 2: dry blending:

In this method, the CMC is dispersed with other dry ingredients, such as sugar, prior to their
addition to aqueous systems. The other particles serve to keep the CMC particles away from
each other. Commonly, one part of CMC is mixed with five to ten parts sugar to effectively prevent
lumping. The dry mix beverage is a classic example of this dispersion technique.

Method 3: dispersion in a water miscible non-solvent:

Cellulose gum may be dispersed in glycerine, ethanol, or propylene glycol and the slurry is then
added to water. An off-shoot of this method is to disperse the gum in corn syrup, and then add the
mixture to water with the aid of agitation.

7
Method 4: mixing device:
Another method for the addition of cellulose gum to food systems in plant operations is the use of
a stainless steel mixing device (figure 14). The gum is fed through a smooth wall funnel into a
water jet eductor, where it is dispersed by the turbulence of water flowing at high velocity. Each
particle is individually wetted out to give a uniform solution. Under optimum conditions, cellulose
gum leaving the eductor is about 80 - 90% hydrated.

ADD THE GUM FIRST! (Figure 15) This is a general rule to follow when adding cellulose gum to
water in all food formulations. Any electrolytes that are dissolved in the water first can greatly
inhibit the hydration of cellulose gum and lower its efficiency.

8
As an example of the importance of order of addition, Figure 16 is a graph of CMC viscosity
versus salt concentration. In one case, the CMC was dissolved in the water before the salt, and
the salt had a minimal effect on the viscosity of the solution. In the other case, the CMC was
dissolved AFTER the salt, and the resulting final viscosity was much lower, especially as the salt
concentration increases.

Figure 17 gives an idea of how cellulose gum is effected by increasingly stronger salt solutions,
and by the uniformity of substitution. Going from distilled water to 4% sodium chloride drops the
viscosity by a factor of about 12 for 7HF, and by about 3 for the more evenly substituted 7H3SF.
The proportions are similar when going to a saturated salt solution (last column).

9
Figure 18 shows the effect of some other ions on the viscosity of a CMC solution. The Aluminum
salt actually increases the viscosity of CMC because it has the steric capability of gelling CMC.
Unfortunately, for taste reasons, this has little application in the food industry.

Figure 20 shows that the viscosity of CMC, like most other water soluble polymers, decreases with
increasing temperature. Under normal conditions, this effect is reversible (ie: raising or lowering
the solution temperature has no permanent effect on the viscosity characteristics of the solution).
However prolonged heating at extremely high temperatures will permanently degrade the cellulose
gum (depolymerization) which results in a viscosity decrease. What this means to the food
technologist is that CMC is not particularly retort stable, even at neutral pH values.

10
Figure 21 indicates that CMC, like most food gums, is pseudoplastic. This means that the
apparent viscosity will decrease at increasing shear rates, because the long molecules will line up
in the direction of the shear, giving less resistance to flow. The effect is totally reversible. As soon
as the shear is stopped, the viscosity returns to its original value because the molecules assume
random positions relative to each other.

CMC is more tolerant to the presence of ethanol than most other food gums (Figure 22). This
makes cellulose gum useful for cordials and other low alcohol content beverages which require
optical transparency.

11
CMC will give a synergistic viscosity increase with other hydrocolloids such as guar or locust bean
gum (Figure 23). If one were to mix a 1% guar solution of 3800 centipoise with a 1% CMC
solution of 4000 centipoise, the net result is not the 3900 centipoise average of the two; it will be
closer to 6500 centipoise. There are more average "collisions per second" between unlike
molecules, which results in this synergistic viscosity increase.

The key functions of cellulose gum in food systems are to provide viscosity / thickening, to
"organize" the water, to form flexible films, and to control the rate and size of crystal growth.

12
The availability of cellulose gum in different viscosity grades, particle sizes, special rheological
grades, and combinations thereof permits tailor-made application of CMC to many different food
systems. The following is a brief discussion of some of these applications:

Cake mixes

CMC is used to improve the moisture retention in cake mixes, as a dried out cake is quite
objectionable organoleptically. High D.S. types are preferred in cake mixes for maximum moisture
binding. CMC also controls batter viscosity, imparts tolerance during mixing, protects against
leavening loss, improves cake volume, and controls the uniformity of the cross sectional grain of
the cake. For ease of mixing, fine grind types of CMC are preferred in cake mixes for rapid entry
into solution. The other formula ingredients provide a dispersion method for the CMC.

Frostings and Icings

CMC may be used in frostings and icings to toughen the film, prevent sticking to the package, and
reduce sugar crystal growth (graininess). In ready-to-spread frostings CMC helps stabilize the
emulsion and adds creaminess. Most important, CMC prevents the icing or frosting from drying
out. Uniformity substituted CMC (S types) are recommended to give a smooth icing or frosting.

Pie fillings

In starch based pie fillings, the addition of a small amount of CMC will prevent cracking control
syneresis and firm the texture. The use of uniformity substituted O types of CMC are preferred for
stability in acidic fillings such as in a lemon pie filling.

Dairy products

CMC was originally pioneered in ice cream and today this application still remains as one of the
largest single uses for the gum. In ice cream CMC prevents ice crystal growth (sandiness),
inhibits lactose crystal growth, imparts mix viscosity and body to the finished product, gives correct
meltdown, and provides freeze/thaw stability (heat shock control). The use of coarse particle size
types of CMC are preferred for ice cream applications (dispersion) because of poor mixing

13
conditions commonly encountered in dairies. CMC is utilized as a stabilizer in many other dairy
products such as egg nog, soft serve ice cream, milk shakes, and ice cream ripples.

Pancake syrup

CMC enjoys widespread use in regular, reduced calorie and dietetic pancake syrups. Here the
excellent clarity, viscosity ability compatibility with sugar and non-caloric characteristics of the gum
are put to good use.

Dry mix beverages

The ability of CMC to hydrate rapidly and viscosity in aqueous systems for body and mouthfeel is
used in instant breakfast drinks instant fruit drinks hot cocoa mixes and low calorie dry mix
beverages. Uniformity substituted low or medium viscosity fine grind types of CMC are most
frequently used in these products in order to minimize "fish eye" formation. High viscosity types of
CMC are not recommended in these products regardless of particle size since higher molecular
weight types take longer to dissolve and are more prone to form fisheyes if dispersion and energy
input (stirring) are not optimum.

Pet foods and animal feed

In semi-moist pet foods, CMC facilitates extrusion, binds moisture, and improves the cosmetic
appearance of the product. In dry gravy-forming pet foods CMC is "dusted" onto tallow coated
"kibble" with other ingredients, so that upon reconstitution a rich viscous shiny gravy evolves.
Another animal food application for CMC is its use as a physical binder in pelleted animal feeds. A
small amount of low viscosity CMC in the product holds the pellet together and prevents
accumulation of fines in the product package during shipment. Additionally, the gum assists the
extrusion process during manufacture of the pellets and helps reduce energy consumption by the
pellet mill.

CMC greatly modifies the behavior of water in sugar solutions (figure 26). Combinations of sugar
and CMC display a significant "boost" in viscosity that is believed to be the consequence of a
crowding mechanism. Cellulose gum decreases the tendency towards syneresis in high sugar
food systems by serving as a water binder. Most importantly, CMC also reduces the rate of sugar

14
crystal growth and crystal size in concentrated sugar systems. This functionality becomes
important in confectionery applications such as fondants (Figure 27 below).

Just as CMC controls sugar crystal growth in confectionery applications, it controls ice crystal
growth in ice cream the same way. Texturally, it is desirable to have a large number of small ice
crystals (smooth) rather than a small number of large ones (sandy).

A few cautions about using cellulose gum in food products: Exposure to UV light and entrained air
in a food system should be minimized to prevent degradation of the gum. Molecular oxygen will
cause the gum to breakdown by a free radical mechanism similar to that, which occurs during the
autoxidation of lipids. The presence of cations (calcium, iron, and aluminum) will accelerate the
process. Therefore it is recommended that a sequestrant such as sodium hexametaphosphate be
used in systems where CMC is exposed to air and cations.

Our next topic is methylcellulose and methylhydroxypropylcellulose.

15
For methylcellulose, some of the hydroxyl groups on the glucose ring have been converted to
methyl ether groups. Note that this makes methylcellulose non-ionic, where CMC was anionic.
Also, the methyl ether groups are far more hydrophobic than the carboxymethyl groups on CMC.

Methylhydroxypropylcellulose has both methyl ether groups and hydroxypropyl groups where
hydroxyl groups used to be on the cellulose backbone. MHPC is also non-ionic like MC.
Hydroxypropyl groups also can be attached to other hydroxypropyl groups ("stacked"), besides
attaching to the glucose ring hydroxyl sites. This can lead to other changes in solution behavior
that we will discuss later on.

16
The Aqualon division of Hercules refers to their MC and MHPC products by the trade name
"Benecel", and it is their nomenclature that will be explained. The letter "M" indicates
methylcellulose, while the letters "MP" indicate methylhydroxypropylcellulose. The first digit
inidcates the average percent by weight of hydroxypropyl groups in the product. The second digit
is the viscosity, and the third digit is the power of ten to multiply the second digit by. For example,
"M043" would be methylcellulose with a viscosity of 4000 centipoise as a 2% solution. "MP823"
would be methylhydroxypropylcellulose containing 8% (w/w) hydroxypropyl groups, and would
have a 2% viscosity of 2000 centipoise.

The unique property of MC and MHPC is thermal gelation. Most gum solutions become thinner
when heated. MC and MHPC solutions do become thinner when heated, but only to a point.
Above that critical temperature, they will gel and become a solid mass. Upon cooling, they will
revert to transparent but viscous solutions again. If heated too far above their gelation point, they
will flocculate (precipitate) and settle out. Upon cooling, the flocculent material will redissolve in
the water.

17
At room temperature, there is a layer of "organized" water molecules surrounding the MC
molecule. This "water of hydration" is associated with the hydroxyls on the cellulose backbone,
and extends out the thickness of several water molecules. This organized water layer is large
enough to prevent the hydrophobic ("water avoiding" or "oil soluble") methyl ether groups from
approaching each other close enough to start clinging together.

As the temperature of the solution is raised, the "organized" water layer around the MC molecules
becomes thinner. This is why the solution initially becomes thinner as it is heated. When the
water layer reaches a certain critical "thinness", the methyl ether groups can now get close
enough to each other to try and cling together to avoid the remaining water (or to minimize entropy
regarding the organized water). These methyl group "clumps" form junction zones, which results
in the buildup of a gel structure, in a manner analogous to the hydrogen bonding together of
unsubstituted regions of CMC molecules to form a thixotropic gel structure.

18
The amount of hydroxypropyl groups will influence the gel point (gelling temperature) of the
methylcellulose. As a general rule, the higher the percentage of HP groups, the higher the gel
point (temperature) and the softer the gel structure. It is assumed that the size of the HP groups
will affect how thin the water layer must be before the methyl groups can cling together.

The concentration of MC or MHPC in water affects the temperature at which the gum precipitates,
or its "flocculation point". It is thought that the increased crowding that accompanies increased
concentration leads to increased statistical odds of inter-chain hydrogen bonding, and thus
precipitation. Most food applications do not call for more than one half percent MC or MHPC, so
this is less of a concern for the food technologist.

19
The key functions of MC and MHPC in food systems are that the gums provide thickening /
viscosity when cold (below body temperature) and can form rigid gels when hot (60 degrees C and
higher). They are good film formers, as most hydrocolloids are, and they create optically
transparent water solutions. Because they are water soluble, the MC films make excellent oil
barriers in deep fat fried foods. Most interesting is the surface activity of MC and MHPC. Usually
we associate whipping agents as being water soluble proteins such as gelatin and egg whites, for
these molecules posses both hydrophilic and hydrophobic areas along their chains. Since MC and
MHPC also posses both hydrophilic and hydrophobic areas along their chains, they make
excellent whipping agents when compared to most other hydrocolloids.

The most well known food applications of MC and MHPC involve deep-frying, where the thermal
gelation of MC and MHPC can lead to greater mechanical strength while hot. Also, there is less
oil pickup in fried foods due to the oil barrier properties of MC and MHPC. This would include all
forms of batter and breaded meat items, onion rings, chicken nuggets, etc. Extruded food also
may benefit from the thermal gelation properties of these hydrocolloids. Whipped / aerated
products can make use of the whipping and self stabilizing properties of the methylcelluloses,
while soups and sauces benefit from the thickening properties. The best quality "veggie burgers"
are made from soy proteins plus MC and carrageenan. The MC provides hot strength to the
burger, while the carrageenan provides gel strength at the lower temperature ranges.

20
Hydroxypropylcellulose has hydroxypropyl groups where hydroxyl groups used to be on the
cellulose backbone. HPC is also non-ionic like MC. Hydroxypropyl groups also can be attached
to other hydroxypropyl groups besides attaching to the glucose ring hydroxyl sites.

The Aqualon division of Hercules refers to their HPC products by the trade name "Klucel", and it is
their nomenclature that will be explained. One gets increasing viscosity going down the list of
designations. Please note that they do not follow alphabetical order.

21
The key functions of HPC in food systems are that it can provide thickening / viscosity when cold.
It is a good film former, as most hydrocolloids are, and can create optically transparent water
solutions. Most interesting is the surface activity of HPC. Usually we associate whipping agents
as being water soluble proteins such as gelatin and egg whites, for these molecules posses both
hydrophilic and hydrophobic areas along their chains. Since HPC also possesses both hydrophilic
and hydrophobic areas along its chains, it makes an excellent whipping agent.

The major current food applications of HPC are as a whipping / stabilizing agent for whipped non-
dairy toppings, and as a surface film agent on confectionery items. Please note that HPC does
not have a gelled state when hot. When an HPC solution is heated to the "gel point", it flocculates
(Precipitates) out of solution. It does redissolve upon cooling of the water.

22
Here is an example of how the type of side chain can affect hydrocolloid properties. In the above
figure there are listed three different cellulose based gums. All three have the same average
backbone length, but all three have different side units. At 25 degrees Celsius, all three of these
gums have the same 1% (w/w) water viscosity in distilled water, as measured with a Brookfield
viscometer. Now, let us heat all three of the 1% water solutions to a temperature of about 70
degrees Celsius. As the 1% CMC solution is heated to 70 degrees Celsius, it becomes thinner,
and the Brookfield viscosity drops to about 1200 centipoise. This is a reversible process. If the
solution is cooled back down to 25C, it will immediately go back to a viscosity of 3000 centipoise
again. The reason for the viscosity drop with increasing temperature is that the layer of
"organized" water molecules around the CMC molecule becomes smaller as the temperature
rises, making collisions with a neighbor somewhat less likely. When the methyl cellulose solution
approaches 70 degrees, it actually changes into a white, opaque, rigid gel that can be cut with a
knife and will retain its shape. As soon as this gel begins to cool off, it will again revert to a
transparent liquid of about 3000 centipoise at 25C. As the hydroxypropylcellulose solution
approaches 70 degrees, it precipitates out of solution and makes a white layer on the bottom of
the container. Upon cooling back down towards 25C., the hydroxypropyl cellulose will begin to
redissolve in the water. So we have three gums with identical backbone structures of cellulose,
but they each have different side chains, which leads to three very different behaviors when the
solutions are heated to 70C

23
In summary, the cellulose derivatives can offer the food technologist a wide range of behaviors
and textures under varied conditions of temperature., and can provide stability under a wide range
of conditions as well.

Andrew C. Hoefler
Brookside Consulting
321 Mill Pond Lane
Oxford, PA 19363
610-932-5167
ahoefler@aol.com

24