Biodegradable Films
Based on Partially Hydrolyzed Corn Starch or Potato Starch
Herbert Sommerfeld and Rijdiger ~ l u m e '
Department of Chemical Education, University of Bielefeld,D-4800 Bielefeld 1, Germany
Renewable raw materials are gaining increasing import-
ance as starting materials for chemical syntheses (13).
Applications that lead to ecologically compatible products
are becoming especially interesting.
The Need for Biodegradable Films
An important renewable raw material is biopolymer
starch. One of the basic properties of starch is its film-
forming ability. In developing chemical modifications that
improve upon this natural ability for industrial and house-
hold applications, attention should be paid to whether the
products retain the original biodegradability (4,5).Thus, it
is advantageous to preserve the native molecular structure
of the starch molecule as much as possible so that decom-
position by enzymes can still occur.
Conventionalpolyolefm films constitute about 2% of nor-
mal household waste, and thus create a disposal problem
if they are not recycled or incinerated (6).Several unsuc-
cessful attempts have been made to improve the photooxi-
dative decomposition of polyolefin films that do not un-
dergo biological degradation. The development of
biodegradable films has made a considerable contribution
to the protection of the environment. Thus, the prepara-
tion of starch-based films is a very promising field of re-
search (7).
Demonstration of the promising developments in starch
chemistry can be done with short and relevant classroom
experiments. Such experiments are useful in encouraging
not only the students' interest in chemistry, but also their
participation in interdisciplinary discussions of related bi-
ological, toxicological, ecological, and economical prob-
lems.
Improving the Quality of the Films
Most corn, potato, and wheat starches comprise
amylopedin at 7045% and amylose at 15-30% (8).The
film-forming ability of starch is principally due to hydro-
gen bonds between the long-chain, unbranched amylose
molecules. The more-globular amylopectin, which disturbs
the crystalline order, improves the strength. However, the
high brittleness due to amylopectin binders the commer-
cial application of simple starch films.
Nevertheless, the chemical derivation of native starch
and the addition of nontoxic plasticizers can both be used
to manufacture films that show satisfactory tensile
strength, flexibility,and transparency for multipie applica-
tions (e.g., as packaging materials). Small molecules that
form hvdroeen bonds with starch. such as water or alco-
hob, afread; exhibit plasticizer effects. However, water or
simple alcohols can not be used satisfactorilv in this a o ~ l i -
cat& due to their high volatility. A better cioice is a 'defi-
nite polyol (e.g., glycerol).
Since they have a high content of hydrophilic alcoholic
hyclroxyl gmups, starch films (in contrast to hydrophobic
polyolefin films) may be colored with water-soluble food
colors without exceeding the limiting values for food addi-
tives established by WHO (9).Films consisting of starch,
glycerol, and food colors are completely nontoxic.
The aualitv of starch films is hiehlv dependent on the
ratio ofamyiose to amylopectin a n i o n th/average molec-
ular weight of the starch. A large percentage of
amylopedin (M, = lo6 to 2 x lo7)is as &advantageous as
a high content of amylose (M, = 4 x lo4 to 2 x lo5). The
acid-catalyzed partial hydrolyzation of native starch can
achieve two mals: decrease the amvlopedin content and
decrease of the average molecular weiiht. The hydrolysis
of the helical amylose molecules is slow compared to the
hydrolysis of amilopectin.
Tensile streneth can be imoroved bv addim comwnents
that cause furtger cross-liAng. An ekample?s diaidehyde
starch. which is obtained bv oxidizing starch with sodium
rneta-periodate (10). Films that contgn dialdehyde starch
are still biodegradable. (Continued on page A152)
Volume 69 Number 5 May 1992 A151
The Modern Student laboratory:
Exploring the Environment
Experimental Section
Experiment 1: Preparation of Starch-Based Films
Required time: 20 min and 1day (for desiccation).
Equipment
f l a s k (100 mL)
heatable magnetic stirrer
oil bath
'thermometer
.plastic sheet (acrylic glass, about 15 x 15 cm2)
4 pipets (2 mL, 3 mL, 20 mL, and 25 mL)
desiccator cabinet, if available
Reagents
corn starch (Merck No. 11686.0250)
or potato starch (Merck No. 1259.0250)
solution of glycerol in distilled water (50 vol%)
distilled water
solutions of food colors in water (1 g1100 mL)
patent blue (Fluka No. 76270)
new-coccine, also called cochineal red (Aldrich No. 19.973-7)
hydrochloric acid (0.1mom)
solution of sodium hydroxide in water (0.1mollL)
Pmcedure
The following ingredients are heated in a flask for ex-
actly 15 min a t 1 0 5 1 1 0 'C and stirred until a homoge-
neous mixture is formed.
2.5 g of corn starch (or 2.5 g of potato starch)
2 mL of glycerol solution
0.2-1 mL of food color solution
3 mL of diluted hydrochloric acid
'20 mL of distilled water (with potato starch, 25 mL)
The hot viscous solution is neutralized by the addition of
3 mL of dilute sodium hydroxide solution. Then it is poured
on a plastic sheet and dried in a desiccator cabinet a t 100-
110 'C for about 1.5 h. After desiccation, a colored, high-
quality starch film can be removed from the sheet. The
drying-time dependson the thickness of the film and
should be observed.
Experiment2: Preparation of Dialdehyde Starch
Required time: 60 min on day 1,and 20 min on day 2.
Caution:Sodium meta-periodate is oxidizing and it is com-
bustible. Handle it with care, as recommended by the manu-
facturer. Dialdehyde starch can be harmful to humans.
Handle with care.
T h e following scheme illustrates t h e formation of
dialdehyde starch.
A152 Journal of Chemical Education
Equipment
flask (100 mL)
magnetic stimr
dropping funnel
filtering material
beaker (100 mL)
Reagents
cam starch (MerckNo. 11686.0250)
or potato starch (Merck No. 1259.0250)
solution of glycerol in water (50 ~01%)
distilled water
sodium me&-periodate(Merck No. 6597.0050)
Procedure
A solution of 5.1 g sodium meta-periodate in 65 mL of
distilled water is slowly added over a period of 1 h to a
stirred mixture that contains 4 g of starch in 20 mL of dis-
tilled water. (When potato starch is used, 25 mL of distilled
water is needed.)
The mixture should be stirred for a n additional 24 h a t
20 'C and then filtered. The residue must be washed three
times with water to remove ionic com~onents.
~
The wet dialdehyde starch mixture, which weighs about
11-.e. is about 754 water. The undried oroduct will be used
in Experiment 4.
Experiment 3: Films with Additional Dialdehyde Starch
Required time: 20 min and 1day (for desiccation).
Equipment
Identical to that used in Experiment 1.
Reagents
Identical to those used in Experiment 1,with the addi-
tion of the dialdehyde starch obtained in Experiment 2.
Procedure
The procedure is similar that used in Experiment 1,
except that the 0.5 g of starch are replaced with 2 g of wet
dialdehyde starch. The resulting film exhibits improved
strength.
Acknowledgment
We thank our collaborators Anja Bergmam and Michael
Kiinsebeck for preparing several starch derivatives and
the BASF AG for the friendly donation of food colors.
Literature Cited
1. Noturwlss. Unfwr (Chmie): Bader,H. J.;Blume,R.,Eda.:1989.47.
2. Sommexfeld. H.:Biume, R.; Bader, H. J.Pror Nofunoh. (Chnie) 1990,2,28-33.
3. Blume. R.: Bader. H. J. Umadfchemls im Emolmmnt: Srnotor:Ran!&rt. 1989.
ion, 1976.
hiatiq R. Bemiller, J. N.:Paschall, E. F. Starch--ChemlsIry and ?kchnalagy;
nis Ress: New York, 1984.
1'8 Eneyclopodio oflndusbial chemistry: Gerhartz, W , Ed.: Weinheim,
. .
Debold, Germany, 1990.
8. Carrer. C. E.: Seymour, R. B. J Chm. Educ. ISM, 64,314318.
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