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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- gen bonds between the long-chain, unbranched amylose
ance as starting materials for chemical syntheses (13). molecules. The more-globular amylopectin, which disturbs
Applications that lead to ecologically compatible products the crystalline order, improves the strength. However, the
are becoming especially interesting. high brittleness due to amylopectin binders the commer-
cial application of simple starch films.
The Need for Biodegradable Films Nevertheless, the chemical derivation of native starch
An important renewable raw material is biopolymer and the addition of nontoxic plasticizers can both be used
starch. One of the basic properties of starch is its film- to manufacture films that show satisfactory tensile
forming ability. In developing chemical modifications that strength, flexibility,and transparency for multipie applica-
improve upon this natural ability for industrial and house- tions (e.g., as packaging materials). Small molecules that
hold applications, attention should be paid to whether the form hvdroeen bonds with starch. such as water or alco-
products retain the original biodegradability (4,5).Thus, it hob, afread; exhibit plasticizer effects. However, water or
is advantageous to preserve the native molecular structure simple alcohols can not be used satisfactorilv in this a o ~ l i -
of the starch molecule as much as possible so that decom- cat& due to their high volatility. A better cioice is a 'defi-
position by enzymes can still occur. nite polyol (e.g., glycerol).
Conventionalpolyolefm films constitute about 2% of nor- Since they have a high content of hydrophilic alcoholic
mal household waste, and thus create a disposal problem hyclroxyl gmups, starch films (in contrast to hydrophobic
if they are not recycled or incinerated (6).Several unsuc- polyolefin films) may be colored with water-soluble food
cessful attempts have been made to improve the photooxi- colors without exceeding the limiting values for food addi-
dative decomposition of polyolefin films that do not un- tives established by WHO (9).Films consisting of starch,
dergo biological degradation. The development of glycerol, and food colors are completely nontoxic.
biodegradable films has made a considerable contribution
to the protection of the environment. Thus, the prepara- The aualitv of starch films is hiehlv dependent on the
tion of starch-based films is a very promising field of re- ratio ofamyiose to amylopectin a n i o n th/average molec-
search (7). ular weight of the starch. A large percentage of
Demonstration of the promising developments in starch amylopedin (M, = lo6 to 2 x lo7)is as &advantageous as
chemistry can be done with short and relevant classroom a high content of amylose (M, = 4 x lo4 to 2 x lo5). The
experiments. Such experiments are useful in encouraging acid-catalyzed partial hydrolyzation of native starch can
not only the students' interest in chemistry, but also their achieve two mals: decrease the amvlopedin content and
participation in interdisciplinary discussions of related bi- decrease of the average molecular weiiht. The hydrolysis
ological, toxicological, ecological, and economical prob- of the helical amylose molecules is slow compared to the
lems. hydrolysis of amilopectin.
Tensile streneth can be imoroved bv addim comwnents
Improving the Quality of the Films that cause furtger cross-liAng. An ekample?s diaidehyde
Most corn, potato, and wheat starches comprise starch. which is obtained bv oxidizing starch with sodium
amylopedin at 7045% and amylose at 15-30% (8).The rneta-periodate (10). Films that contgn dialdehyde starch
film-forming ability of starch is principally due to hydro- are still biodegradable. (Continued on page A152)

Volume 69 Number 5 May 1992 A151


The Modern Student laboratory:
Exploring the Environment

Experimental Section Equipment


Experiment 1: Preparation of Starch-Based Films flask (100 mL)
magnetic stimr
Required time: 20 min and 1day (for desiccation). dropping funnel
filtering material
Equipment beaker (100 mL)
f l a s k (100 mL)
heatable magnetic stirrer Reagents
oil bath cam starch (MerckNo. 11686.0250)
'thermometer or potato starch (Merck No. 1259.0250)
.plastic sheet (acrylic glass, about 15 x 15 cm2) solution of glycerol in water (50 ~01%)
4 pipets (2 mL, 3 mL, 20 mL, and 25 mL) distilled water
desiccator cabinet, if available sodium me&-periodate(Merck No. 6597.0050)
Reagents Procedure
corn starch (Merck No. 11686.0250) A solution of 5.1 g sodium meta-periodate in 65 mL of
or potato starch (Merck No. 1259.0250) distilled water is slowly added over a period of 1 h to a
solution of glycerol in distilled water (50 vol%) stirred mixture that contains 4 g of starch in 20 mL of dis-
distilled water
solutions of food colors in water (1 g1100 mL) tilled water. (When potato starch is used, 25 mL of distilled
patent blue (Fluka No. 76270) water is needed.)
new-coccine, also called cochineal red (Aldrich No. 19.973-7) The mixture should be stirred for a n additional 24 h a t
hydrochloric acid (0.1mom) 20 'C and then filtered. The residue must be washed three
solution of sodium hydroxide in water (0.1mollL) times with water to remove ionic com~onents.
~

The wet dialdehyde starch mixture, which weighs about


Pmcedure 11-.e. is about 754 water. The undried oroduct will be used
The following ingredients are heated in a flask for ex- in Experiment 4.
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) Experiment 3: Films with Additional Dialdehyde Starch
2 mL of glycerol solution
0.2-1 mL of food color solution Required time: 20 min and 1day (for desiccation).
3 mL of diluted hydrochloric acid Equipment
'20 mL of distilled water (with potato starch, 25 mL)
Identical to that used in Experiment 1.
The hot viscous solution is neutralized by the addition of
3 mL of dilute sodium hydroxide solution. Then it is poured Reagents
on a plastic sheet and dried in a desiccator cabinet a t 100- Identical to those used in Experiment 1,with the addi-
110 'C for about 1.5 h. After desiccation, a colored, high- tion of the dialdehyde starch obtained in Experiment 2.
quality starch film can be removed from the sheet. The
drying-time dependson the thickness of the film and Procedure
should be observed. The procedure is similar that used in Experiment 1,
except that the 0.5 g of starch are replaced with 2 g of wet
Experiment2: Preparation of Dialdehyde Starch dialdehyde starch. The resulting film exhibits improved
Required time: 60 min on day 1,and 20 min on day 2. strength.
Caution:Sodium meta-periodate is oxidizing and it is com-
bustible. Handle it with care, as recommended by the manu- Acknowledgment
facturer. Dialdehyde starch can be harmful to humans. We thank our collaborators Anja Bergmam and Michael
Handle with care. Kiinsebeck for preparing several starch derivatives and
T h e following scheme illustrates t h e formation of the BASF AG for the friendly donation of food colors.
dialdehyde starch.
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.
9. Bader, H. J.; Some.rfeld. H. Pror Notunuisa. (Chamlsj 1988,3,1&20.
10. Mdhods in Corbohydmte chemistrv: Whistler, R. L., Ed.:Academic Preaa: New

A152 Journal of Chemical Education