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STRCH Based Applications

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5506

New Approaches to Research on Cereal Carbohydrates, edited by R.D. Hill and L. Munck 191
Elsevier Science Publishers B.V., Amsterdam, 1985 - Printed in The Netherlands
NEW STARCH-BASED POLYMER TECHNOLOGIES
F. H. OTEY
Northern Regional Research Center, Agricultural Research Service, U.S.
Department of Agriculture, Peoria, Illinois 61604
INTRODUCTION
For several years our Center has conducted both fundamental and applied
research to develop new products from starch. These research efforts have
resul ted in several new technologies and new markets for starch and have
led to additional applied research by the private sector in many countries.
Some of the earlier efforts involved depolymerization of starch into heat- and
alkali-stable polyols, and subsequent studies involved how to use these as
polyol initiators to make new polymers for polyurethane (ref.l), alkyd resin
(ref.2), surfactant (ref.3), adhesive, and food emulsifier applications. With
the advent of the petroleum crisis, these studies and those of other research
laboratories have b e c o m ~ of special interest to the private sector seeking to
find less expensive renewable substitutes for petroleum. The O.S-billion-lb/yr
U. S. ri gid polyurethane foam industry has converted to carbohydrate-based
polyol initiators, and the surfactant and alkyd industries are looking more
toward natural polyols and away from petroleum. One U.S. starch company
recently constructed a 30-mil1ion-lb/yr facility for making starch-derived.
polyo1s; a company executive sai d that such starch-deri ved chemi cal s coul d
prove to be a S-billion-lb/yr market, primarily for foams, films, adhesives,
and pa i nts (ref. 4).
Thi s paper describes concepts, approaches, and some resul ts of current
programs at our Center on new starch polymer technologies to provide
biodegradable plastics, membranes, and controlled release systems. The research
is intended to help reduce pollution associated with the disposal of
nondegradable plastics, to lower the level and frequency of application and
improve safety in handling of agricultural chemicals, and to reduce U.S.
dependence on imported petroleum. Approaches are toward polymer bl endi ng,
grafting, and crosslinking of starch in aqueous systems and away from major
modifi cat ions wi th toxic and fl ammab1e chemi ca1s that mi ght di scourage the
private sector from making the technology available to consumers. The studies
192
take advantage of the natural polymeric structure and the superior
bi odegradabil ity of starch over most petro 1eum-derived polymers. The water
sensitivity of starch offers advantages for some applications, whereas for
some others thi s water sens itivity must be reduced. Although the amylose
fraction of starch would offer certain property advantages, we have restricted
our current programs to whole starch because of the cost and the restricted
availability of amylose.
STARCH IN PLASTICS
Different approaches have been investigated for using starch in plastics.
One approach, using starch as a dry particulate filler, has been investigated
extensively both in plastics and in rubber. A second approach, the one we are
now investigating, involves using gelatinized starch molecules as an integral
part of the polymeric structure. Starch is inherently water sensitive; upon
drying it becomes rigid and brittle from the high densities of molecular
branching and hydrogen bonding. The embrittlement imparted to plastics by
. starch is overcome to various degrees by adding plasticizers and other materials
that retard association of starch molecules.
Plasticized ~ ~
The only successful plasticizers for starch films are water-soluble
materials that help retain moisture in the film. Water dispersions of starch
and plasticizers, such as glycerol, can be cast into flexible films. However,
they have no industrial potential as nonsupported films because they deteriorate
in water and become very brittle at ambient conditions. Film flexibility and
water resistance were greatly improved by adding polyvinyl alcohol (PVA) to
the starch-glycerol formulation and by coating the films with a thin layer of
either poly(vinyl chloride) or a vinyl idene chloride-acrylonitrile copolymer
(ref.S).
Noncoated films made with PVA, glycerol plasticizer, and high levels of
starch rapidly lose flexibility. For example, films made with 22.4% glycerol,
15% PVA, and 60% starch could be stretched or elongated 146% after aging
1 day, but they elongated only 9% after 10 days aging. Increasing the glycerol
level to 30% and decreasing the starch level to 51% increased elongation to
300%, but effects of the plasticizer decreased rapidly with aging. In contrast,
mixed polyol plasticizers composed of either 3 parts glycol glucoside or
sorbitol to 1 part glycerol yielded films with % elongation stabilized for
more than a year. Similar results were observed when CaC1
2
was added to a
glycerol plasticized film.
The reason polyols plasticize starch films is not fully known but may
relate to their moisture-holding power or humectancy. At high moisture content,
193
sufficient water is present to satisfy the hydrogen-bonding sites of starch.
As films age and lose moisture, added polyols may satisfy some of the bonding
capacity but in so doing they lose some of their humectancy.
These studies on plasticized starch-PYA films led to the commercialization
of water-soluble films made by band-casting aqueous solutions of water-soluble
starch, PYA, and plasticizers. These films are now used to produce laundry
bags for use by hospitals to protect patients and hospital personnel against
the danger of cross contamination from soiled linens. Laundry sealed in the
bags is placed directly into washing machines, where the bag dissolves.
Nonplasticized ili!:!! ~
The blending of starch with synthetic polymers and water-soluble
plasticizers is proving very successful for specific applications of starch-
based film because the benefits of water solubility exceed the high cost of
film casting, where production rate is slow and large amounts of processing
water must be evaporated. For 1arger sca1e app1i cat ions, water-extractable
plasticizers must be avoided, and the formulation must be adaptable to the
more economically feasible extrusion blowing technique now used for most
synthetic film production. Also, at least 40% starch must be present to
achieve a desirable rate of biodegradation. We are having considerable success
in achieving these objectives by blending gelatinized starch with poly(ethylene-
Q-acrylic acid) (EAA).
--(CHZCHZ)X--{CHzyH)y-
COZH
Films made from this system require no plasticizer, yet they remain flexible
even after exposure to water and drying. Fig. la is a photomicrograph of a
dry, flexible film that contained SO% partially gelatinized starch and SO%
EAA. The starch appears reasonably well dispersed into the film. Although
the mechanism is not ~ n o w n , we envision that as internal bonding within starch
molecules is reduced during gelatinization and extrusion, new bonds aTe formed
wi th the EAA carboxyl group that retard retrogradation of the starch. The
dried film may correlate with the theory of "molecular slippage" relief of
locally high stresses associated with elastomer reinforcement. In essence,
that theory asserts that physically adsorbed chains on filler particles slip
qr break the physical bond in areas of high stress to more uniformly distribute
stress throughout the sample (ref.6). Under stress, the starch chains may not
be broken or totally di sbonded from the EAA since other portions of a "s1i pped"
chain can remain hydrogen bonded to the EAA.
194
Fig. 1. Scanning electron photomicrographs of film specimens containing 50%
starch and 50% EAA. Samples photographed at 10,000 times. (a) No NaOH added
(b) 5 pph NaOH added.
In addition to eliminating the requirement for water-soluble plasticizers,
the starch-EAA system is the first reported blend with up to 50-60% starch
that can be extrusion-blown into films. These films have several potential
applications where biodegradability is important, such as in agricultural
mulch. Carnell (ref.7) reports the following consumption of plastic mulch,
million lb/yr: Japan, 250; U.S., 100; France, 84; and Israel, 16. Plastic
mulch is used on such crops as tomatoes, peppers, melons, and sweet corn to
help control soil moisture and temperature, reduce nutrient leaching, prevent
weed growth, and increase crop yields by 50 to 350%. Polyethylene film does
not degrade between growing seasons, so it must be removed from the field and
buried or burned at an estimated cost of S100 per acre.
Semipermeable membranes
Adding a strong alkali, such as sodium hydroxide, to the starch-EAA blend
will cause extrusion-blown films from the blend to have semipermeable
characteristics. The photomicrograph (Fig. Ib) of a dry film specimen, made
from a blend that contained on a dry basis 50% starch, 50% EAA, and 5 parts
per hundred (pph) NaOH, illustrates a much better dispersion of the starch
than was achieved without alkali (Fig. la). Preliminary evaluation of the
films is being made with a rotating dialysis cell. This cell consists of two
hollowed-out discs that are clamped together, with the membrane to be tested
200..-------;---,-----,
160
160
140
Q 120
Q
::
100
<31'"
":/":/
.5 60
60
40
20
200 240 260
195
Fig. 2. Relation of
vs. t/v for
six solutes diffusing
through a film
contai ni ng 40% starch
(fitted by equation 2).
(1)
separating the two discs. One of the resulting cylindrical compartments is
partially filled with water and the other with solution, and while diffusion
proceeds the cell is rotated about its horizontal shaft at a constant speed of
73.5 rpm. Observed membrane permeabilities (Po) are calculated from the rate
of change of the solute concentrations in both compartments. using the following
equation:

p = ----=---:=----
o

where is the measured difference in concentration between the two chambers
at conveniently separated times of measurement t
1
and t
2
A is the membrane
area through which transport takes place, and Va and Vb are the total volumes
of each of the two chambers. The equation predicts a straight line passing
through the origin where ln is plotted against t/v, when the volumes
ln (IlCo/IlC) = b (t/v) (2)
on each side of the film are kept equal but are decreased during time studies
due to sampling for analyses. Experimental data from a film containing 40%
starCh, 60% EAA, and 5 pph NaOH are plotted in Fig. 2 where three or four
samples of the solutions on each side of the film were analyzed after various
times of dialyses. Area of the exposed film was 78.5 cm
2
and 1.5% solute
concentrations were used for each run. The data are consistent with a zero
theoretical intercept.
Figure 2 clearly demonstrates that the films allow small molecules of
urea and HaCl ions to 'di ffuse many times faster than larger sugar molecules.
196
The slower permeability rate for NaCl relative to. urea may be attributable to
charges on the film.
Table 1 lists additional permeability data, where the NaCl and urea rates
were determi ned on i ndi vi dua1 runs and the sugars and a1ani ne were run as
mixtures and analyzed by HPLC. Increasing the starch level or adding water-
soluble materials such as ethylene glycol or sucrose increased diffusion rate.
The water-soluble additives are readily leached during film soaking, so their
primary functions may be to increase the starch to EAA ratio in the soaked
film; they also improve ease of film preparation. Most of the data reported
in Table 1 were collected on film samples that had soaked in water for several
days. We have since learned that transport rates decrease during water soaking
for up to 30 days. However, studi es underway revea1 that the fi 1ms can be
treated with alkaline solutions to restore the transport rate and in some
instances increase the rate by severalfold.
TABLE 1
Permeability data for several solutes
a
Starch/"
EAA, %b NaCl Urea
Po X 10
6
(cm/sec)
Glucose Fructose Sucrose Raffinose Alanine
60140 31. 6 53 6.3 2.9 2.5
40/60 5.1 17.5 0.9 1.2 0.6 0.1 2.4
20/80 0.01
40/60
c
4.6 1.0 1.1 0.4 0.1 2.2
40/40
c
,d
11.S 33.6 2.0 2.3 0.9 0.2 4.0
40/30
e
34.7 112 5.1 5.7 2.6 1.3 6.5
aSolute concentrations were 1. 5%; ran at atm pressure and room
temperature.
b5 parts NaOH per 100 parts of starch-EAA were added to
formulation.
CHydroxyethylated starch.
dFormulation contained 20% ethylene glycol.
eContained 30% sucrose.
It is too early to predict how starch-based films may fit into the
projected $1.7 billion per yr semipermeable membrane field (ref.S).
Economically, they have a good chance of commercial acceptance because they
can be produced by the low-cost extrusion blowing technique, and formulation
variables allow a wide r-ange of transport rates and pore size. Current
197
application of membranes include: gas separation, such as separating hydrogen
from ammonia; wastewater treatment; controlled release of materials, such as
drugs; and various dialysis applications for the kidney machine or, industrially,
for separating large molecules from smaller ones.
lli.!:!l graft copo1ymers
Fanta and Doane (ref.9) have reviewed starch grafts for several
applications. The grafting of synthetic polymers onto starch provides another
approach for maki ng starch-based pl ast i cs. Although the starch in these
systems may be broadly classified as a filler, the flexibility allowed in
their preparation offers numerous alternatives to conventional fillers. Also,
unlike most filler systems, the polymer is covalently bonded to the starch.
The synthesis procedures are very simple and may prove to be the most economical
method for making plastics from starch. To prepare the graft copolymers, free
radicals are initiated onto the starch, either chemically or by irradiation,
and then are allowed to react with polymerizable vinyl or acrylic monomers.
The choice of free radical initiation method depends on the particular monomer
or combination of monomers to be polymerized. Free radical initiation for
styrene grafting is best achieved with a cobalt 60 source, whereas ceric
ammonium nitrate is more commonly used for grafting acrylonitrile and the
acrylates. In essence, the grafting procedure consists of stirring at room
temperature for about 3 hr a water slurry of monomer and initiated starch in
the absence of oxygen; then the starch graft copolymer is filtered off.
Graft polymerizations have, for the most part, been carried out in water,
either with granular, unswo11en starch or with starch that has been gelatinized
by heating. For grafting onto gelatinized starch, aqueous slurries of starch
are heated for 30 min at 85-90
o
C and then cooled to 25C prior to adding the
monomer. A1 though gelati nization swell sand di srupts starch granu1 es, the
polysaccharide is still largely insoluble in the aqueous medium; polymerizations
can thus be viewed as taking place onto an insoluble substrate. Only a limited
number of polymerizations have been run with water solutions of starch.
Fanta ~ sl. (ref.10) made an interesting observation on the location of
grafts within a starch granule that clearly distinguishes these systems from
conventi ona1 fi 11 ers. Scanni ng electron micrographs of starch-g-
polyacry1onitri1e made with unswol1en starch revealed that grafting took place
largely on the surface of the granule with low add-on of 22% graft, whereas
with a 44% add-on the grafting took place throughout the granule interior.
Similar studies suggest that styrene grafting occurs primarily on the surface
of starch granules. These types of studies have not yet been made for the
acry1ates.
198
TIME
TOXIC TO CROP
.. TOXIC TO weeo
\
\
\
\
\
\
Fi g. 3. Idea1i zed
release profile for
controlled release (CR)
of an encapsuIated
herbi ci de .
Although melt flow is inhibited by the rigid starch matrix, extrusion
processing of starch-g-thermoplastic copolymers will yield continuous plastics,
provided the %add-on is about 50% or higher and the extrusion temperature is
considerably above Tg of the thermoplastic component. Plastic formation
occurs by fusing together individual heat-softened granules of graft copolymer
under the high pressures encountered in the extruder die. Scanning electron
micrographs of extruded plastics clearly show the fused granule structure
(ref.ll); the negligible die swell observed in extruded plastics also provides
evidence that graft copolymers were never in the molten state.
STARCH-BASED CONTROLLED RELEASE SYSTEM
Research at our Center is demonstrating that starch is a promi sing
encapsulating matrix for controll;"ng the release of chemical pesticides to
improve safety in handling and to reduce losses of pesticides in the environment
due to volatility, leaching, and decomposition by light.
Approaches to the work have required a wide range of both technical and
economical considerations. We chose to use approved commercial pesticides and
to avoid chemical modifications, such as covalently bonding the pesticides
onto starch, because such products would probably require approval as a new
pesticide--a very expensive and slow process.
Secondly, for herbicides, the release profile should approach the idealized
system illustrated in Fig. 3 (dotted line) under a wide range of field conditions
where soil moisture, temperature, pH, and microorganisms vary considerably.
Ideally, the herbicide must be released at a rate sufficient to control the
target weed but slow enough to avoid phytotoxicity to the crop. Also, because
of variations in weather conditions and weed germination rates, an effective
level of herbicide must be available for several weeks to avoid multiple
199
(Xanthide)
(Xanthate) Starch-OH + CS
Z
+ NaOH
S (0)
II
Starch-OCSNa
applications, which sometimes are required for conventional formulation.
Further demands on the system occur when farmers prefer to apply the herbicide
in the fall or to delay soil incorporation. Most conventional formulations
now require immediate soil incorporation to reduce losses from evaporation and
photodegradation. Finally, research approaches were needed for trapping the
pesticide within a starch particle suitable for agronomic applications.
Encapsulation is achieved by incorporating pesticides into an aqueous
dispersion of gelatinized starch and then insolubilizing the starch by various
crosslinking methods. In our first method, the starch was covalently crosslinked
as starch xanthide (ref.lZ). An alkali dispersion of starch was reacted with
carbon disulfide to form starch xanthate (0.1-0.3 OS). Pesticides were
emulsified into this dispersion, and then an oxidant was added to crosslink
the starch xanthate to an i nso1ub 1e starch xanthi de, whi ch entrapped the
pesticide in small cells within granular particles.
S
II
Starch-OCSNa
S S
II II
------------
Extensive greenhouse and field studies revealed that starch encapsulation
great ly reduces evaporation, mi crobi a1 degradati on, photodegradati on, and
leaching rate of active ingredients over those for nonencapsulated pesticides.
Yet, the release of active agent was sufficient to provide adequate pest
control. Because of this controlled release, even volatile pesticides do not
require immediate soil incorporation.
More recently, we have found that pesti ci des can be encapsul ated by
adding either calcium chloride (ref.13) or boric acid (ref.14) to the starch-
a1kal i -pesti ci de di spersi ons. Scanni ng electron mi crographs and 1aboratory
release studies indicated that these precipitated starch complexes contain the
pesticide trapped in small cells, very much as was found for the xanthide
encapsulation. In extensive field and greenhouse studies, these latter products
have proven very effective in extending the life of herbicides.
Although there are performance differences between the three classes of
products, the borate products are currently emergi ng as the most feasi b1e
because of processi ng advantages. In contrast to the xanthate process, no
carbon disulfide is required. Also, the borate method is conducted with lower
levels of water, so that no effluent water must be discharged and the final
product contains all of the added pesticide. In both the xanthate and calcium
methods, fi 1trates contai ni ng si gnifi cant amounts of both pesti ci de and
formulating chemicals must be recycled or the chemicals must be removed before
the processing water can be discharged into streams.
200
We are now di recti ng more effort toward release mechani sm and factors
that affect release of pesticides from the starch-based systems. Moisture is
one important factor. Generally, when I-g samples are wetted with 2-mL portions
of water and allowed to dry for 24 h, 5-10% of active agent is released, and
this rate of loss will continue with repeated wetting and drying cycles. The
method of starch crosslinking appears to have little affect on these release
rates. When the products are agi tated wi th more water, especi ally in the
presence of a starch-degrading enzyme, the covalently bonded xanthide system
is more stable. For example, when O.I-g samples were agitated with 2 ml
water, buffered to pH 6 for 4 h, 2%, 16%, and 22% of the active agent was
released from the xanthide, calcium, and borate products, respectively. With
a-amylase present in these systems, nearly 100% of the active agent is released
in 1-2 h from the borate and calcium products, but only 14% was released in
4 h from the xanthi de product. Release rate also decreases wi th increased
particle size. Efforts are underway to improve methods for determining release
rates anq to more fully understand the effects of matrix structure on release
properties. A better knowledge of these systems would allow design of
appropriate formulations for specific applications and greatly enhance
acceptance of this technology for broad-scale agronomic use.
REFERENCES
1 R.H. leitheiser, C.N. Impola, R.J. Reid and F.H. Otey, Ind. Eng. Chem.
Prod. Res. Dev., 5 (1966) 276-282.
2 W.J. McKillip, J.N. Kellen, C.N. Impola, R.W. 8uckney and F.H. Otey, J.
Paint Technol., 42 (1970) 312-319.
3 P.E. Throckmorton, R.R. Egan, D. Aelony, G.K. M u l b e r r ~ and F.H. Otey, J.
Am. Oil Chem. Soc., 51 (1974) 486-494.
4 Anon. , Chem. Eng., 90 (1983) 27.
5 F.H. Otey, A.M. Mark, C.l. Mehltretter and C.R. Russell, Ind. Eng. Chem.
Prod. Res. Dev., 13 (1974) 90-92.
6 T.P. Abbott, C. James and F.H. Otey, J. Appl. Polym. Sci., 23 (1979)
1223-123l.
7 D. Carnell, Am. Veg. Grower, May 1983, pp. 54-57.
8 Anon., Chem. Week, 133 (1983) 22.
9 G.F. Fanta and W.M. Doane, Properties and Uses of Modified Starches, CRC
Press, Inc., 80ca Raton, Florida, in press.
10 G.F. Fanta, F.l. Baker, R.C. Burr, \II.M. Doane and C.R. Russell, Starke,
25 (1973) 157-161.
11 C.l. Swanson, G.F. Fanta and E.B. Bagley, Polym. Compos., 5 (1984) 52-59.
12 W.M. Doane, B.S. Shasha and C.R. Russell, ACS Symp. Ser., 53 (1977)
74-83.
13 B.S. Shasha, D. Trimnell and F.H. Otey, J. Polym. Sci., Polym. Chem. Ed.,
19 (1981) 1891-1899.
14 D. Trimnell, B.S. Shasha, R.E. Wing and F.H. Otey, J. Appl. Polym. Sci.,
27 (1982) 3919-3928.

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